1-(heterocyclic carbonyl) piperidines

ABSTRACT

The present invention relates to fungicidal 1-(heterocyclic carbonyl) piperidines and their thiocarbonyl derivatives, their process of preparation and intermediate compounds for their preparation, their use as fungicides, particularly in the form of fungicidal compositions and methods for the control of phytopathogenic fungi of plants using these compounds or their compositions.

CROSS REFERENCE TO RELATED APPLICATION(S)

The present application is a 35 U.S.C. §371 national phase conversion of PCT/EP2011/068287 filed on Oct. 20, 2011, which claims priority to European Application No. 10356029.8 filed on Oct. 21, 2010 and U.S. Provisional Application No. 61/414,612 filed on Nov. 17, 2010. Applicants claim priority to the foregoing patent applications. The PCT International Application was published in the English language.

The present invention relates to fungicidal 1-(heterocyclic carbonyl) piperidines and their thiocarbonyl derivatives, their process of preparation and intermediate compounds for their preparation, their use as fungicides, particularly in the form of fungicidal compositions and methods for the control of phytopathogenic fungi of plants using these compounds or their compositions.

In international patent application DE3641343 certain fungicidal heterocyclylcarbonylimidazoles are generically embraced in a broad disclosure of numerous compounds of the following formula:

wherein Y can represent a phenyl ring, n can be equal to 2 to 6, m can be equal to 1 to 2, and R can represent various substituent among which a methoxy group. However, there is no disclosure or suggestion in this document of any such derivative wherein the imidazole moiety can be replaced by a carbo-linked 5-membered heterocyclyl group.

In international patent application WO-2007/039781 certain inhibitors of the glutamate receptor are generically embraced in a broad disclosure of numerous compounds of the following formula:

wherein R can represent a heteroaryl group, Z can represent a —(CH₂)n- group where n can be 1 or 2, X₁ and X₂ are different and can be selected from N or O, Q can be N or a —CH— group, and Y₁ and Y₂ can represent various substituents. However, there is no disclosure or suggestion in this document of any use of such derivatives as antifungal or antimicrobial compounds.

In international patent application WO-2007/039782 certain inhibitors of the glutamate receptor are generically embraced in a broad disclosure of numerous compounds of the following formula:

wherein R can represent a heteroaryl group, Z can represent a —(CH₂)n- group where n can be 1 or 2, and Y₁ and Y₂ can represent various substituents. However, there is no disclosure or suggestion in this document of any use of such derivatives as antifungal or antimicrobial compounds.

It is always of high interest in the field of agrochemicals to use pesticidal compounds more active than the compounds already known by the man ordinary skilled in the art whereby reduced amounts of compound can be used whilst retaining equivalent efficacy.

Furthermore, the provision of new pesticidal compounds with a higher efficacy strongly reduces the risk of appearance of resistant strains in the fungi to be treated.

We have now found a new family of compounds which show enhanced fungicidal activity over the general known family of such compounds.

Accordingly, the present invention provides a 1-(heterocyclic [thio]carbonyl) piperidine derivative of formula (I)

wherein

-   -   A represents a carbo-linked, unsaturated or partially saturated,         5-membered heterocyclyl group that can be substituted by up to         four groups R that can be the same or different;     -   T represents O or S;     -   n represents 0, 1 or 2;     -   Q¹ represents a bond; O; S; SO; or SO₂;     -   B represents a phenyl ring that can be substituted by up to 5         groups X which can be the same or different; a naphthyl ring         that can be substituted by up to 7 groups X which can be the         same or different; or a saturated, partially saturated or         unsaturated, monocyclic or fused bicyclic 4-, 5-, 6-, 7-, 8-,         9-, 10-membered ring comprising from 1 up to 4 heteroaroms         selected in the list consisting of N, O, S, that can be         substituted by up to 6 groups X which can be the same or         different;     -   X represents a halogen atom; nitro; cyano; isonitrile; hydroxy;         amino; sulfanyl; pentafluoro-λ⁶-sulfanyl; formyl; formyloxy;         formylamino; substituted or non-substituted         (hydroxyimino)-C₁-C₈-alkyl; substituted or non-substituted         (C₁-C₈-alkoxyimino)-C₁-C₈-alkyl; substituted or non-substituted         (C₂-C₈-alkenyloxyimino)-C₁-C₈-alkyl; substituted or         non-substituted (C₂-C₈-alkynyloxyimino)-C₁-C₈-alkyl; substituted         or non-substituted (benzyloxyimino)-C₁-C₈-alkyl; carboxy;         carbamoyl; N-hydroxycarbamoyl; carbamate; substituted or         non-substituted C₁-C₈-alkyl; C₁-C₈-halogenoalkyl having 1 to 5         halogen atoms; substituted or non-substituted C₂-C₈-alkenyl;         C₂-C₈-halogenoalkenyl having 1 to 5 halogen atoms; substituted         or non-substituted C₂-C₈-alkynyl; C₂-C₈-halogenoalkynyl having 1         to 5 halogen atoms; substituted or non-substituted C₁-C₈-alkoxy;         C₁-C₈-halogenoalkoxy having 1 to 5 halogen atoms; substituted or         non-substituted C₁-C₈-alkylsulfanyl; C₁-C₈-halogenoalkylsulfanyl         having 1 to 5 halogen atoms; substituted or non-substituted         C₁-C₈-alkylsulfinyl; C₁-C₈-halogenoalkylsulfinyl having 1 to 5         halogen atoms; substituted or non-substituted         C₁-C₈-alkylsulfonyl; C₁-C₈-halogenoalkylsulfonyl having 1 to 5         halogen atoms; substituted or non-substituted C₁-C₈-alkylamino;         substituted or non-substituted di-C₁-C₈-alkylamino; substituted         or non-substituted C₂-C₈-alkenyloxy; C₂-C₈-halogenoalkenyloxy         having 1 to 5 halogen atoms; substituted or non-substituted         C₃-C₈-alkynyloxy; C₂-C₈-halogenoalkynyloxy having 1 to 5 halogen         atoms; substituted or non-substituted C₃-C₇-cycloalkyl;         C₃-C₇-halogenocycloalkyl having 1 to 5 halogen atoms;         substituted or non-substituted (C₃-C₇-cycloalkyl)-C₁-C₈-alkyl;         substituted or non-substituted (C₃-C₇-cycloalkyl)-C₂-C₈-alkenyl;         substituted or non-substituted (C₃-C₇-cycloalkyl)-C₂-C₈-alkynyl;         substituted or non-substituted tri(C₁-C₈)alkylsilyl; substituted         or non-substituted tri(C₁-C₈)alkylsilyl-C₁-C₈-alkyl; substituted         or non-substituted C₁-C₈-alkylcarbonyl;         C₁-C₈-halogenoalkylcarbonyl having 1 to 5 halogen atoms;         substituted or non-substituted C₁-C₈-alkylcarbonyloxy;         C₁-C₈-halogenoalkylcarbonyloxy having 1 to 5 halogen atoms;         substituted or non-substituted C₁-C₈-alkylcarbonylamino;         C₁-C₈-halogenoalkyl-carbonylamino having 1 to 5 halogen atoms;         substituted or non-substituted C₁-C₈-alkoxycarbonyl;         C₁-C₈-halogenoalkoxycarbonyl having 1 to 5 halogen atoms;         substituted or non-substituted C₁-C₈-alkyloxycarbonyloxy;         C₁-C₈-halogenoalkoxycarbonyloxy having 1 to 5 halogen atoms;         substituted or non-substituted C₁-C₈-alkylcarbamoyl; substituted         or non-substituted di-C₁-C₈-alkylcarbamoyl; substituted or         non-substituted C₁-C₈-alkylaminocarbonyloxy; substituted or         non-substituted di-C₁-C₈-alkylaminocarbonyloxy; substituted or         non-substituted N—(C₁-C₈-alkyl)hydroxy carbamoyl; substituted or         non-substituted C₁-C₈-alkoxycarbamoyl; substituted or         non-substituted N—(C₁-C₈-alkyl)-C₁-C₈-alkoxycarbamoyl; aryl that         can be substituted by up to 6 groups Q which can be the same or         different; C₁-C₈-arylalkyl that can be substituted by up to 6         groups Q which can be the same or different; C₂-C₈-arylalkenyl         that can be substituted by up to 6 groups Q which can be the         same or different; C₂-C₈-arylalkynyl that can be substituted by         up to 6 groups Q which can be the same or different; aryloxy         that can be substituted by up to 6 groups Q which can be the         same or different; arylsulfanyl that can be substituted by up to         6 groups Q which can be the same or different; arylamino that         can be substituted by up to 6 groups Q which can be the same or         different; C₁-C₈-arylalkyloxy that can be substituted by up to 6         groups Q which can be the same or different;         C₁-C₈-arylalkylsulfanyl that can be substituted by up to 6         groups Q which can be the same or different; or         C₁-C₈-arylalkylamino that can be substituted by up to 6 groups Q         which can be the same or different; or     -   two substituent X together with the consecutive carbon atoms to         which they are linked can form a 5- or 6-membered, saturated         carbocycle or saturated heterocycle, which can be substituted by         up to four groups Q which can be the same or different;     -   Z¹ and Z² independently represent a hydrogen atom; a halogen         atom; cyano; substituted or non-substituted C₁-C₈-alkyl;         C₁-C₈-halogenoalkyl having 1 to 5 halogen atoms; substituted or         non-substituted C₁-C₈-alkoxy; substituted or non-substituted         C₁-C₈-alkylsulfanyl; or substituted or non-substituted         C₁-C₈-alkoxycarbonyl; or     -   two substituents Z¹ and Z², together with the carbon atom to         which they are linked can form a 3-, 4-, 5- or 6-membered         saturated carbocycle that can be substituted by up to four         C₁-C₈-alkyl groups;     -   Z³ represents a hydrogen atom; or substituted or non-substituted         C₁-C₈-alkyl;     -   Q independently represents a halogen atom; cyano; nitro;         substituted or non-substituted C₁-C₈-alkyl; C₁-C₈-halogenoalkyl         having 1 to 9 halogen atoms that can be the same or different;         substituted or non-substituted C₁-C₈-alkoxy;         C₁-C₈-halogenoalkoxy having 1 to 9 halogen atoms that can be the         same or different; substituted or non-substituted         C₁-C₈-alkylsulfanyl; C₁-C₈-halogenoalkylsulfanyl having 1 to 9         halogen atoms that can be the same or different; substituted or         non-substituted tri(C₁-C₈)alkylsilyl; substituted or         non-substituted tri(C₁-C₈)alkylsilyl-C₁-C₈-alkyl; substituted or         non-substituted (C₁-C₈-alkoxyimino)-C₁-C₈-alkyl; substituted or         non-substituted (benzyloxyimino)-C₁-C₈-alkyl;     -   R independently represents hydrogen atom; halogen atom; nitro;         cyano; hydroxy; amino; sulfanyl; pentafluoro-λ⁶-sulfanyl;         substituted or non-substituted (C₁-C₈-alkoxyimino)-C₁-C₈-alkyl;         substituted or non-substituted (benzyloxyimino)-C₁-C₈-alkyl;         substituted or non-substituted C₁-C₈-alkyl; C₁-C₈-halogenoalkyl         having 1 to 5 halogen atoms; substituted or non-substituted         C₂-C₈-alkenyl; C₂-C₈-halogenoalkenyl having 1 to 5 halogen         atoms; substituted or non-substituted C₂-C₈-alkynyl;         C₂-C₈-halogenoalkynyl having 1 to 5 halogen atoms; substituted         or non-substituted C₁-C₈-alkoxy; C₁-C₈-halogenoalkoxy having 1         to 5 halogen atoms; substituted or non-substituted         C₁-C₈-alkylsulfanyl; C₁-C₈-halogenoalkylsulfanyl having 1 to 5         halogen atoms; substituted or non-substituted         C₁-C₈-alkylsulfinyl; C₁-C₈-halogenoalkylsulfinyl having 1 to 5         halogen atoms; substituted or non-substituted         C₁-C₈-alkylsulfonyl; C₁-C₈-halogenoalkylsulfonyl having 1 to 5         halogen atoms; substituted or non-substituted C₁-C₈-alkylamino;         substituted or non-substituted di-C₁-C₈-alkylamino; substituted         or non-substituted C₂-C₈-alkenyloxy; substituted or         non-substituted C₃-C₈-alkynyloxy; substituted or non-substituted         C₃-C₇-cycloalkyl; C₃-C₇-halogenocycloalkyl having 1 to 5 halogen         atoms; substituted or non-substituted tri(C₁-C₈)alkylsilyl;         substituted or non-substituted C₁-C₈-alkylcarbonyl;         C₁-C₈-halogenoalkylcarbonyl having 1 to 5 halogen atoms;         substituted or non-substituted C₁-C₈-alkoxycarbonyl;         C₁-C₈-halogenoalkoxycarbonyl having 1 to 5 halogen atoms;         substituted or non-substituted C₁-C₈-alkylcarbamoyl; substituted         or non-substituted di-C₁-C₈-alkylcarbamoyl; phenoxy;         phenylsulfanyl; phenylamino; benzyloxy; benzylsulfanyl; or         benzylamino;         as well as its salts, N-oxides, metal complexes, metalloid         complexes and optically active isomers provided that the         following compounds are excluded:

-   (2,5-dimethyl-3-furyl){2-[2-(3-methylphenyl)-2H-tetrazol-5-yl]piperidin-1-yl}methanone

-   (5-bromo-2-furyl){2-[2-(3-bromophenyl)-2H-tetrazol-5-yl]piperidin-1-yl}methanone

-   (5-bromo-2-furyl){2-[2-(3-chlorophenyl)-2H-tetrazol-5-yl]piperidin-1-yl}methanone

-   (5-bromo-2-furyl){2-[2-(3-methoxyphenyl)-2H-tetrazol-5-yl]piperidin-1-yl}methanone

-   (5-bromo-2-thienyl){2-[2-(3-chlorophenyl)-2H-tetrazol-5-yl]piperidin-1-yl}methanone

-   (5-methyl-2-furyl){2-[2-(3-methylphenyl)-2H-tetrazol-5-yl]piperidin-1-yl}methanone

-   {2-[2-(3,5-dichlorophenyl)-2H-tetrazol-5-yl]piperidin-1-yl}(5-methyl-2-furyl)methanone

-   {2-[2-(3,5-dimethoxyphenyl)-2H-tetrazol-5-yl]piperidin-1-yl}(2-thienyl)methanone

-   {2-[2-(3-bromophenyl)-2H-tetrazol-5-yl]piperidin-1-yl}(2-furyl)methanone

-   {2-[2-(3-bromophenyl)-2H-tetrazol-5-yl]piperidin-1-yl}(2-thienyl)methanone

-   {2-[2-(3-bromophenyl)-2H-tetrazol-5-yl]piperidin-1-yl}(4,5-dimethyl-2-furyl)methanone

-   {2-[2-(3-bromophenyl)-2H-tetrazol-5-yl]piperidin-1-yl}(5-methyl-2-furyl)methanone

-   {2-[2-(3-bromophenyl)-2H-tetrazol-5-yl]piperidin-1-yl}(5-methyl-2-thienyl)methanone

-   {2-[2-(3-bromophenyl)-2H-tetrazol-5-yl]piperidin-1-yl}[5-(methylsulfanyl)-2-thienyl]methanone

-   {2-[2-(3-chlorophenyl)-2H-tetrazol-5-yl]piperidin-1-yl}(1,2,3-thiadiazol-4-yl)methanone

-   {2-[2-(3-chlorophenyl)-2H-tetrazol-5-yl]piperidin-1-yl}(1,3-dimethyl-1H-pyrazol-5-yl)methanone

-   {2-[2-(3-chlorophenyl)-2H-tetrazol-5-yl]piperidin-1-yl}(1,5-dimethyl-1H-pyrazol-3-yl)methanone

-   {2-[2-(3-chlorophenyl)-2H-tetrazol-5-yl]piperidin-1-yl}(2,4-dimethyl-1,3-thiazol-5-yl)methanone

-   {2-[2-(3-chlorophenyl)-2H-tetrazol-5-yl]piperidin-1-yl}(2-methyl-3-furyl)methanone

-   {2-[2-(3-chlorophenyl)-2H-tetrazol-5-yl]piperidin-1-yl}(3-furyl)methanone

-   {2-[2-(3-chlorophenyl)-2H-tetrazol-5-yl]piperidin-1-yl}(4,5-dimethyl-2-furyl)methanone

-   {2-[2-(3-chlorophenyl)-2H-tetrazol-5-yl]piperidin-1-yl}(4-methoxy-3-thienyl)methanone

-   {2-[2-(3-chlorophenyl)-2H-tetrazol-5-yl]piperidin-1-yl}(4-methyl-1,3-thiazol-5-yl)methanone

-   {2-[2-(3-chlorophenyl)-2H-tetrazol-5-yl]piperidin-1-yl}(5-methyl-1,2-oxazol-3-yl)methanone

-   {2-[2-(3-chlorophenyl)-2H-tetrazol-5-yl]piperidin-1-yl}(5-methyl-2-thienyl)methanone

-   {2-[2-(3-chlorophenyl)-2H-tetrazol-5-yl]piperidin-1-yl}[5-(methylsulfanyl)-2-thienyl]methanone

-   {2-[2-(3-fluorophenyl)-2H-tetrazol-5-yl]piperidin-1-yl}(5-methyl-2-furyl)methanone

-   {2-[2-(3-fluorophenyl)-2H-tetrazol-5-yl]piperidin-1-yl}(5-methyl-2-thienyl)methanone

-   {2-[2-(3-methoxyphenyl)-2H-tetrazol-5-yl]piperidin-1-yl}(2-thienyl)methanone

-   {2-[2-(3-methylphenyl)-2H-tetrazol-5-yl]piperidin-1-yl}(3-methyl-2-thienyl)methanone

-   {2-[2-(3-methylphenyl)-2H-tetrazol-5-yl]piperidin-1-yl}(3-thienyl)methanone

-   {2-[2-(3-methylphenyl)-2H-tetrazol-5-yl]piperidin-1-yl}(5-methyl-2-thienyl)methanone

-   {2-[3-(3,4-dimethylphenyl)-1,2,4-oxadiazol-5-yl]piperidin-1-yl}(3-methyl-2-thienyl)methanone

-   {2-[3-(3-chlorophenyl)-1,2,4-oxadiazol-5-yl]piperidin-1-yl}(2-furyl)methanone

-   {2-[3-(3-chlorophenyl)-1,2,4-oxadiazol-5-yl]piperidin-1-yl}(3-furyl)methanone

-   {2-[3-(3-methoxyphenyl)-1,2,4-oxadiazol-5-yl]piperidin-1-yl}(2-thienyl)methanone

-   {2-[3-(3-methoxyphenyl)-1,2,4-oxadiazol-5-yl]piperidin-1-yl}(5-methyl-2-thienyl)methanone

-   {2-[3-(3-methylphenyl)-1,2,4-oxadiazol-5-yl]piperidin-1-yl}(2-thienyl)methanone

-   2-furyl{2-[2-(3-methylphenyl)-2H-tetrazol-5-yl]piperidin-1-yl}methanone

-   2-furyl{2-[3-(3-methoxyphenyl)-1,2,4-oxadiazol-5-yl]piperidin-1-yl}methanone

-   2-furyl{2-[3-(3-methylphenyl)-1,2,4-oxadiazol-5-yl]piperidin-1-yl}methanone

-   3-(5-{1-[(5-bromo-2-thienyl)carbonyl]piperidin-2-yl}-2H-tetrazol-2-yl)benzonitrile

-   3-(5-{1-[(5-methyl-2-thienyl)carbonyl]piperidin-2-yl}-1,2,4-oxadiazol-3-yl)benzonitrile

-   3-(5-{1-[(5-methyl-2-thienyl)carbonyl]piperidin-2-yl}-2H-tetrazol-2-yl)benzonitrile

-   3-[5-(1-{[5-(methylsulfanyl)-2-thienyl]carbonyl}piperidin-2-yl)-2H-tetrazol-2-yl]benzonitrile

-   3-{5-[1-(2-furoyl)piperidin-2-yl]-2H-tetrazol-2-yl}benzonitrile

-   3-{5-[1-(2-thienylcarbonyl)piperidin-2-yl]-2H-tetrazol-2-yl}benzonitrile

-   3-{5-[1-(3-furoyl)piperidin-2-yl]-1,2,4-oxadiazol-3-yl}benzonitrile

-   3-{5-[1-(3-furoyl)piperidin-2-yl]-2H-tetrazol-2-yl}benzonitrile

-   3-{5-[1-(4,5-dimethyl-2-furoyl)piperidin-2-yl]-2H-tetrazol-2-yl}benzonitrile

-   3-{5-[1-(5-methyl-2-furoyl)piperidin-2-yl]-2H-tetrazol-2-yl}benzonitrile

-   3-furyl{2-[3-(3-methylphenyl)-1,2,4-oxadiazol-5-yl]piperidin-1-yl}methanone

For the compounds according to the invention, the following generic terms are generally used with the following meanings:

-   -   halogen means fluorine, bromine, chlorine or iodine.         -   carboxy means —C(═O)OH;         -   carbonyl means —C(═O)—;         -   carbamoyl means —C(═O)NH₂;         -   N-hydroxycarbamoyl means —C(═O)NHOH;         -   SO represents a sulfoxide group;         -   SO₂ represents a sulfone group;     -   an alkyl group, an alkenyl group and an alkynyl group as well as         moieties containing these terms, can be linear or branched;     -   the aryl moiety contained in an aryl group, an arylalkyl group,         an arylalkenyl group and an arylalkynyl group as well as         moieties containing these terms, can be a phenyl group that can         be substituted by up to 5 groups Q which can be the same or         different, a naphthyl group that can be substituted by up to 7         groups Q which can be the same or different or a pyridyl group         that can be substituted by up to 4 groups Q which can be the         same or different;     -   heteroatom means sulfur, nitrogen or oxygen.     -   in the case of an amino group or the amino moiety of any other         amino-comprising group, substituted by two substituent that can         be the same or different, the two substituent together with the         nitrogen atom to which they are linked can form a heterocyclyl         group, preferably a 5- to 7-membered heterocyclyl group, that         can be substituted or that can include other hetero atoms, for         example a morpholino group or piperidinyl group.     -   unless indicated otherwise, a group or a substituent that is         substituted according to the invention can be substituted by one         or more of the following groups or atoms: a halogen atom, a         nitro group, a hydroxy group, a cyano group, an amino group, a         sulfanyl group, a pentafluoro-λ⁶-sulfanyl group, a formyl group,         a formyloxy group, a formylamino group, a carbamoyl group, a         N-hydroxycarbamoyl group, a carbamate group, a         (hydroxyimino)-C₁-C₆-alkyl group, a C₁-C₈-alkyl, a         tri(C₁-C₈-alkyl)silyl-C₁-C₈-alkyl, C₁-C₈-cycloalkyl,         tri(C₁-C₈-alkyl)silyl-C₁-C₈-cycloalkyl, a C₁-C₈-halogenoalkyl         having 1 to 5 halogen atoms, a C₁-C₈-halogenocycloalkyl having 1         to 5 halogen atoms, a C₂-C₈-alkenyl, a C₂-C₈-alkynyl, a         C₂-C₈-alkenyloxy, a C₂-C₈-alkynyloxy, a C₁-C₈-alkylamino, a         di-C₁-C₈-alkylamino, a C₁-C₈-alkoxy, a C₁-C₈-halogenoalkoxy         having 1 to 5 halogen atoms, a C₁-C₈-alkylsulfanyl, a         C₁-C₈-halogenoalkylsulfanyl having 1 to 5 halogen atoms, a         C₂-C₈-alkenyloxy, a C₂-C₈-halogenoalkenyloxy having 1 to 5         halogen atoms, a C₃-C₈-alkynyloxy, a C₃-C₈-halogenoalkynyloxy         having 1 to 5 halogen atoms, a C₁-C₈-alkylcarbonyl, a         C₁-C₈-halogenoalkylcarbonyl having 1 to 5 halogen atoms, a         C₁-C₈-alkylcarbamoyl, a di-C₁-C₈-alkylcarbamoyl, a         N—C₁-C₈-alkyloxycarbamoyl, a C₁-C₈-alkoxycarbamoyl, a         N—C₁-C₈-alkyl-C₁-C₈-alkoxycarbamoyl, a C₁-C₈-alkoxycarbonyl, a         C₁-C₈-halogenoalkoxycarbonyl having 1 to 5 halogen atoms, a         C₁-C₈-alkylcarbonyloxy, a C₁-C₈-halogenoalkylcarbonyloxy having         1 to 5 halogen atoms, a C₁-C₈-alkylcarbonylamino, a         C₁-C₈-halogenoalkylcarbonylamino having 1 to 5 halogen atoms, a         C₁-C₈-alkylaminocarbonyloxy, a di-C₁-C₈-alkylaminocarbonyloxy, a         C₁-C₈-alkyloxycarbonyloxy, a C₁-C₈-alkylsulfinyl, a         C₁-C₈-halogenoalkylsulfinyl having 1 to 5 halogen atoms, a         C₁-C₈-alkylsulfonyl, a C₁-C₈-halogenoalkylsulfonyl having 1 to 5         halogen atoms, a C₁-C₈-alkylaminosulfamoyl, a         di-C₁-C₈-alkylaminosulfamoyl, a (C₁-C₆-alkoxyimino)-C₁-C₆-alkyl,         a (C₁-C₆-alkenyloxyimino)-C₁-C₆-alkyl, a         (C₁-C₆-alkynyloxyimino)-C₁-C₆-alkyl, a 2-oxopyrrolidin-1-yl,         (benzyloxyimino)-C₁-C₆-alkyl, C₁-C₈-alkoxyalkyl,         C₁-C₈-halogenoalkoxyalkyl having 1 to 5 halogen atoms,         benzyloxy, benzylsulfanyl, benzylamino, phenoxy, phenylsulfanyl,         or phenylamino.

Any of the compounds of the present invention can exist in one or more optical or chiral isomer forms depending on the number of asymmetric centres in the compound. The invention thus relates equally to all the optical isomers and to their racemic or scalemic mixtures (the term “scalemic” denotes a mixture of enantiomers in different proportions) and to the mixtures of all the possible stereoisomers, in all proportions. The diastereoisomers and/or the optical isomers can be separated according to the methods which are known per se by the man ordinary skilled in the art.

Any of the compounds of the present invention can also exist in one or more geometric isomer forms depending on the number of double bonds in the compound. The invention thus relates equally to all geometric isomers and to all possible mixtures, in all proportions. The geometric isomers can be separated according to general methods, which are known per se by the man ordinary skilled in the art.

Any of the compounds of the present invention can also exist in one or more geometric isomer forms depending on the relative position (syn/anti or cis/trans) of the substituents of ring B. The invention thus relates equally to all syn/anti (or cis/trans) isomers and to all possible syn/anti (or cis/trans) mixtures, in all proportions. The syn/anti (or cis/trans) isomers can be separated according to general methods, which are known per se by the man ordinary skilled in the art.

Any of the compounds of formula (I) wherein X represents a hydroxy, a sulfanyl group or an amino group may be found in its tautomeric form resulting from the shift of the proton of said hydroxy, sulfanyl or amino group. Such tautomeric forms of such compounds are also part of the present invention. More generally speaking, all tautomeric forms of compounds of formula (I) wherein X represents a hydroxy, a sulfanyl group or an amino group, as well as the tautomeric forms of the compounds which can optionally be used as intermediates in the preparation processes and which will be defined in the description of these processes, are also part of the present invention.

Preferred compounds according to the invention are compounds of formula (I) wherein A is selected in the list consisting of:

-   -   a heterocycle of formula (A¹)

wherein: R¹ to R³ that can be the same or different represent a hydrogen atom; a halogen atom; substituted or non-substituted C₁-C₅-alkyl; C₁-C₅-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different; substituted or non-substituted C₁-C₅-alkoxy or C₁-C₅-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different;

-   -   a heterocycle of formula (A²)

wherein: R⁴ to R⁶ that can be the same or different represent a hydrogen atom; a halogen atom; substituted or non-substituted C₁-C₅-alkyl; C₁-C₅-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different; substituted or non-substituted C₁-C₅-alkoxy or C₁-C₅-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different;

-   -   a heterocycle of formula (A³)

wherein: R⁷ represents a hydrogen atom; a halogen atom; substituted or non-substituted C₁-C₅-alkyl; C₁-C₅-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different; substituted or non-substituted C₁-C₅-alkoxy or C₁-C₅-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different; R⁸ represents a hydrogen atom or a substituted or non-substituted C₁-C₅-alkyl;

-   -   a heterocycle of formula (A⁴)

wherein: R⁹ to R¹¹ that can be the same or different represent a hydrogen atom; a halogen atom; substituted or non-substituted C₁-C₅-alkyl; amino; substituted or non-substituted C₁-C₅-alkoxy; substituted or non-substituted C₁-C₅-alkylsulfanyl; C₁-C₅-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different or C₁-C₅-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different;

-   -   a heterocycle of formula (A⁵)

wherein: R¹² and R¹³ that can be the same or different represent a hydrogen atom; a halogen atom; substituted or non-substituted C₁-C₅-alkyl; substituted or non-substituted C₁-C₅-alkoxy; amino; C₁-C₅-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different or C₁-C₅-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different; R¹⁴ represents a hydrogen atom; a halogen atom; substituted or non-substituted C₁-C₅-alkyl; substituted or non-substituted C₁-C₅-alkoxy; amino; C₁-C₅-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different or C₁-C₅-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different;

-   -   a heterocycle of formula (A⁶)

wherein: R¹⁵ represents a hydrogen atom; a halogen atom; a cyano; substituted or non-substituted C₁-C₅-alkyl; substituted or non-substituted C₁-C₅-alkoxy; C₁-C₅-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different or C₁-C₅-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different; R¹⁶ and R¹⁸ that can be the same or different represent a hydrogen atom; a halogen atom; substituted or non-substituted C₁-C₅-alkoxycarbonyl; substituted or non-substituted C₁-C₅-alkyl; C₁-C₅-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different or C₁-C₅-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different; R¹⁷ represent a hydrogen atom or substituted or non-substituted C₁-C₅-alkyl;

-   -   a heterocycle of formula (A⁷)

wherein: R¹⁹ represents a hydrogen atom or a C₁-C₅-alkyl R²⁰ to R²² that can be the same or different represent a hydrogen atom; a halogen atom; substituted or non-substituted C₁-C₅-alkyl or C₁-C₅-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different;

-   -   a heterocycle of formula (A⁸)

wherein: R²³ represents a hydrogen atom; a halogen atom; substituted or non-substituted C₁-C₅-alkyl or C₁-C₅-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different; R²⁴ represents a hydrogen atom or substituted or non-substituted C₁-C₅-alkyl or C₁-C₅-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different;

-   -   a heterocycle of formula (A⁹)

wherein: R²⁵ represents a hydrogen atom; a halogen atom; substituted or non-substituted C₁-C₅-alkyl or C₁-C₅-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different; R²⁶ represents a hydrogen atom; substituted or non-substituted C₁-C₅-alkyl or C₁-C₅-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different;

-   -   a heterocycle of formula (A¹⁰)

wherein: R²⁷ represents a hydrogen atom; a halogen atom; substituted or non-substituted C₁-C₅-alkyl or C₁-C₅-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different; R²⁸ represents a hydrogen atom; a halogen atom; substituted or non-substituted C₁-C₅-alkyl; C₁-C₅-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different; C₁-C₅-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different; amino; substituted or non-substituted C₁-C₅-alkylamino or substituted or non-substituted di(C₁-C₅-alkyl)amino;

-   -   a heterocycle of formula (A¹¹)

wherein: R²⁹ represents a hydrogen atom; a halogen atom; substituted or non-substituted C₁-C₅-alkyl; substituted or non-substituted C₁-C₅-alkoxy; C₁-C₅-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different or C₁-C₅-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different; R³⁰ represents a hydrogen atom; a halogen atom; substituted or non-substituted C₁-C₅-alkyl; C₁-C₅-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different; C₁-C₅-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different; amino; substituted or non-substituted C₁-C₅-alkylamino or substituted or non-substituted di(C₁-C₅-alkyl)amino;

-   -   a heterocycle of formula (A¹²)

wherein: R³¹ represents a hydrogen atom or a substituted or non-substituted C₁-C₅-alkyl R³² represents a hydrogen atom; a halogen atom; substituted or non-substituted C₁-C₅-alkyl or C₁-C₅-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different; R³³ represents a hydrogen atom; a halogen atom; a nitro; substituted or non-substituted C₁-C₅-alkyl; substituted or non-substituted C₁-C₅-alkoxy; C₁-C₅-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different or C₁-C₅-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different;

-   -   a heterocycle of formula (A¹³)

wherein: R³⁴ represents a hydrogen atom; a halogen atom; substituted or non-substituted C₁-C₅-alkyl; substituted or non-substituted C₃-C₅-cycloalkyl; C₁-C₅-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different; substituted or non-substituted C₁-C₅-alkoxy; substituted or non-substituted C₂-C₅-alkynyloxy or C₁-C₅-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different; R³⁵ represents a hydrogen atom; a halogen atom; substituted or non-substituted C₁-C₅-alkyl; a cyano; substituted or non-substituted C₁-C₅-alkoxy; substituted or non-substituted C₁-C₅-alkylsulfanyl; C₁-C₅-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different; C₁-C₅-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different; amino; substituted or non-substituted C₁-C₅-alkylamino or substituted or non-substituted di(C₁-C₅-alkyl)amino; R³⁶ represents a hydrogen atom or substituted or non-substituted C₁-C₅-alkyl;

-   -   a heterocycle of formula (A¹⁴)

wherein: R³⁷ and R³⁸ that can be the same or different represent a hydrogen atom; a halogen atom; substituted or non-substituted C₁-C₅-alkyl; C₁-C₅-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different; substituted or non-substituted C₁-C₅-alkoxy or a substituted or non-substituted C₁-C₅-alkylsulfanyl; R³⁹ represents a hydrogen atom or substituted or non-substituted C₁-C₅-alkyl;

-   -   a heterocycle of formula (A¹⁵)

wherein: R⁴⁰ and R⁴¹ that can be the same or different represent a hydrogen atom; a halogen atom; substituted or non-substituted C₁-C₅-alkyl or C₁-C₅-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different;

-   -   a heterocycle of formula (A¹⁶)

wherein: R⁴² and R⁴³ that can be the same or different represent a hydrogen atom; a halogen atom; substituted or non-substituted C₁-C₅-alkyl; C₁-C₅-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different or amino;

-   -   a heterocycle of formula (A¹⁷)

wherein: R⁴⁴ and R⁴⁵ that can be the same or different represent a hydrogen atom; a halogen atom; substituted or non-substituted C₁-C₅-alkyl or C₁-C₅-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different;

-   -   a heterocycle of formula (A¹⁸)

wherein: R⁴⁷ represents a hydrogen atom; a halogen atom; substituted or non-substituted C₁-C₅-alkyl or C₁-C₅-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different; R⁴⁶ represents a hydrogen atom; a halogen atom; substituted or non-substituted C₁-C₅-alkyl; C₁-C₅-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different or substituted or non-substituted C₁-C₅-alkylsulfanyl;

-   -   a heterocycle of formula (A¹⁹)

wherein: R⁴⁹ and R⁴⁸ that can be the same or different represent a hydrogen atom; a halogen atom; substituted or non-substituted C₁-C₅-alkyl; substituted or non-substituted C₁-C₅-alkoxy; C₁-C₅-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different or C₁-C₅-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different;

-   -   a heterocycle of formula (A²⁹)

wherein: R⁵⁰ and R⁵¹ that can be the same or different represent a hydrogen atom; a halogen atom; substituted or non-substituted C₁-C₅-alkyl; substituted or non-substituted C₁-C₅-alkoxy; C₁-C₅-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different or C₁-C₅-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different;

-   -   a heterocycle of formula (A²¹)

wherein: R⁵² represents a hydrogen atom; a halogen atom; substituted or non-substituted C₁-C₅-alkyl or C₁-C₅-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different.

-   -   a heterocycle of formula (A²²)

wherein: R⁵³ represents a hydrogen atom; a halogen atom; substituted or non-substituted C₁-C₅-alkyl or C₁-C₅-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different.

-   -   a heterocycle of formula (A²³)

wherein: R⁵⁴ and R⁵⁶ that can be the same or different represent a hydrogen atom; a halogen atom; substituted or non-substituted C₁-C₅-alkyl or C₁-C₅-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different; R⁵⁵ represents a hydrogen atom or substituted or non-substituted C₁-C₅-alkyl;

-   -   a heterocycle of formula (A²⁴)

wherein: R⁵⁷ and R⁵⁹ that can be the same or different represent a hydrogen atom; a halogen atom; substituted or non-substituted C₁-C₅-alkyl or C₁-C₅-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different; R⁵⁸ represents a hydrogen atom or substituted or non-substituted C₁-C₅-alkyl;

-   -   a heterocycle of formula (A²⁵)

wherein: R⁶⁰ and R⁶¹ that can be the same or different represent a hydrogen atom; a halogen atom; substituted or non-substituted C₁-C₅-alkyl or C₁-C₅-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different; R⁶² represents a hydrogen atom or substituted or non-substituted C₁-C₅-alkyl;

-   -   a heterocycle of formula (A²⁶)

wherein: R⁶⁵ represents a hydrogen atom; a halogen atom; substituted or non-substituted C₁-C₅-alkyl; substituted or non-substituted C₃-C₅-cycloalkyl; C₁-C₅-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different; substituted or non-substituted C₁-C₅-alkoxy; substituted or non-substituted C₂-C₅-alkynyloxy or C₁-C₅-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different; R⁶³ represents a hydrogen atom; a halogen atom; substituted or non-substituted C₁-C₅-alkyl; a cyano; substituted or non-substituted C₁-C₅-alkoxy; substituted or non-substituted C₁-C₅-alkylsulfanyl; C₁-C₅-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different; C₁-C₅-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different; amino; substituted or non-substituted C₁-C₅-alkylamino or di(C₁-C₅-alkyl)amino; R⁶⁴ represents a hydrogen atom or substituted or non-substituted C₁-C₅-alkyl.

More preferred compounds according to the invention are compounds of formula (I) wherein A is selected in the list consisting of A²; A⁶; A¹⁰ and A¹³ as herein-defined.

Even more preferred compounds according to the invention are compounds of formula (I) wherein A represents A¹³ wherein R³⁴ represents a substituted or non-substituted C₁-C₅-alkyl, C₁-C₅-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different; substituted or non-substituted C₁-C₅-alkoxy; R³⁵ represents a hydrogen atom or a halogen atom and R³⁶ represents a substituted or non-substituted C₁-C₅-alkyl.

Even more preferred compounds according to the invention are compounds of formula (I) wherein A represents A¹³ wherein R³⁴ represents C₁-C₅-alkyl, C₁-C₅-halogenoalkyl comprising up to 3 halogen atoms that can be the same or different; R³⁵ represents a hydrogen atom; a chlorine atom; or a fluorine atom; and R³⁶ represents a methyl.

Other preferred compounds according to the invention are compounds of formula (I) wherein T represents O.

Other preferred compounds according to the invention are compounds of formula (I) wherein n represents 0 or 1.

Other preferred compounds according to the invention are compounds of formula (I) wherein Q¹ represents a bond or an oxygen atom; other more preferred compounds according to the invention are compounds of formula (I) wherein Q¹ represents a bond.

Other preferred compounds according to the invention are compounds of formula (I) wherein B represents a substituted or non-substituted phenyl ring; a substituted or non-substituted naphthyl ring; a substituted or non-substituted pyridyl ring; a substituted or non-substituted thienyl ring; or a substituted or non-substituted benzothienyl ring. More preferred compounds according to the invention are compounds of formula (I) wherein B represents a substituted or non-substituted phenyl ring; other more preferred compounds according to the invention are compounds of formula (I) wherein B represents a substituted or non-substituted naphthyl ring.

Other preferred compounds according to the invention are compounds of formula (I) wherein X independently represents a halogen atom; substituted or non-substituted C₁-C₅-alkyl; C₁-C₈-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different; substituted or non-substituted C₁-C₅-alkoxy or C₁-C₅-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different; or wherein two consecutive substituents X together with the phenyl ring form a substituted or non substituted 1,3-benzodioxolyl or 1,4-benzodioxanyl ring.

Other preferred compounds according to the invention are compounds of formula (I) wherein Z¹ and Z² independently represents a hydrogen atom, a halogen, substituted or non-substituted C₁-C₈-alkyl or substituted or non-substituted C₁-C₈-alkoxy.

Other preferred compounds according to the invention are compounds of formula (I) wherein Z³ represents a hydrogen atom.

The above mentioned preferences with regard to the substituents of the compounds according to the invention can be combined in various manners. These combinations of preferred features thus provide sub-classes of compounds according to the invention. Examples of such sub-classes of preferred compounds according to the invention are:

-   -   preferred features of A with preferred features of T, Q¹, B, n,         Z¹ to Z³, X and/or R;     -   preferred features of T with preferred features of A, Q¹, B, n,         Z¹ to Z³, X and/or R;     -   preferred features of Q¹ with preferred features of A, T, B, n,         Z¹ to Z³, X and/or R;     -   preferred features of B with preferred features of A, T, Q¹, n,         Z¹ to Z³, X and/or R;     -   preferred features of n with preferred features of A, T, Q¹, B,         Z¹ to Z³, X and/or R;     -   preferred features of Z¹ with preferred features of A, T, Q¹, B,         n, Z¹, Z³, X and/or R;     -   preferred features of Z² with preferred features of A, T, Q¹, B,         n, Z¹, Z³, X and/or R;     -   preferred features of Z³ with preferred features of A, T, Q¹, B,         n, Z¹, Z², X and/or R;     -   preferred features of X with preferred features of A, T, Q¹, B,         n, Z¹, to Z³ and/or R;     -   preferred features of R with preferred features of A, T, Q¹, B,         n, Z¹ to Z³ and/or X;

In these combinations of preferred features of the substituents of the compounds according to the invention, the said preferred features can also be selected among the more preferred features of each of A, T, Q¹, B, n, Z¹, Z², Z³, X and R so as to form most preferred subclasses of compounds according to the invention.

The present invention also relates to a process for the preparation of the compound of formula (I).

Thus, according to a further aspect of the present invention there is provided a process P1 for the preparation of a compound of formula (I) as herein-defined and wherein T represents O and that comprises reaction of a piperidine of formula (II) or one of its salts:

wherein Z¹, Z², Z³, n, Q¹ and B are as herein-defined; with a carboxylic acid derivative of formula (III):

wherein A is as herein-defined and L¹ represents a leaving group selected in the list consisting of a halogen atom, a hydroxyl group, —OR^(a), —OC(═O)R^(a), R^(a) being a substituted or non-substituted C₁-C₆-alkyl, a substituted or non-substituted C₁-C₆-haloalkyl, a benzyl, 4-methoxybenzyl or pentafluorophenyl group, or a group of formula O—C(═O)A; in the presence of a catalyst and in the presence of a condensing agent in case L¹ represents a hydroxyl group, and in the presence of an acid binder in case L¹ represents a halogen atom.

Piperidines of formula (II) wherein n is equal to 0 can be prepared by deprotonation of N-Boc-piperidine and transmetallation of the anion by a zinc salt followed by a palladium coupling with (het)aryl bromides and further Boc deprotection (Organic Letters (2008), 10 (17), 3923-3925). Piperidines of formula (II) wherein n is equal to 1 or 2 can be prepared by hydrogenation of the corresponding 2-(het)arylmethyl or 2-(het)arylethylpyridine (Helvetica Chimica Acta (1954), 37, 2133).

Carboxylic acid derivatives of formula (III) can be prepared by known processes.

In case L¹ represents a hydroxy group, the process according to the present invention is conducted in the presence of condensing agent. Suitable condensing agent may be selected in the non limited list consisting of acid halide former, such as phosgene, phosphorous tribromide, phosphorous trichloride, phosphorous pentachloride, phosphorous trichloride oxide or thionyl chloride; anhydride former, such as ethyl chloroformate, methyl chloroformate, isopropyl chloroformate, isobutyl chloroformate or methanesulfonyl chloride; carbodiimides, such as N,N′-dicyclohexylcarbodiimide (DCC) or other customary condensing agents, such as phosphorous pentoxide, polyphosphoric acid, N,N′-carbonyl-diimidazole, 2-ethoxy-N-ethoxycarbonyl-1,2-dihydroquinoline (EEDQ), triphenylphosphine/tetrachloro-methane, 4-(4,6-dimethoxy[1.3.5]-triazin-2-yl)-4-methylmorpholinium chloride hydrate, bromo-tripyrrolidinophosphoniumhexafluorophosphate or propanephosphonic anhydride (T3P).

The process according to the present invention is conducted in the presence of a catalyst. Suitable catalyst may be selected in the list consisting of 4-dimethyl-aminopyridine, 1-hydroxy-benzotriazole or dimethylformamide.

In case L¹ represents a halogen atom, the process according to the present invention is conducted in the presence of an acid binder. Suitable acid binders for carrying out process P1 according to the invention are in each case all inorganic and organic bases that are customary for such reactions. Preference is given to using alkaline earth metal, alkali metal hydride, alkali metal hydroxides or alkali metal alkoxides, such as sodium hydroxide, sodium hydride, calcium hydroxide, potassium hydroxide, potassium tert-butoxide or other ammonium hydroxide, alkali metal carbonates, such as cesium carbonate, sodium carbonate, potassium carbonate, potassium bicarbonate, sodium bicarbonate, alkali metal or alkaline earth metal acetates, such as sodium acetate, potassium acetate, calcium acetate and also tertiary amines, such as trimethylamine, triethylamine, diisopropylethylamine, tributylamine, N,N-dimethylaniline, pyridine, N-methylpiperidine, N,N-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicyclo-nonene (DBN) or diazabicycloundecene (DBU).

It is also possible to work in the absence of an additional condensing agent or to employ an excess of the amine component, so that it simultaneously acts as acid binder agent.

According to a further aspect according to the invention, there is provided a process P2 for the preparation of a compound of formula (I) wherein T represents S, starting from a compound of formula (I) wherein T represents O and illustrated according to the following reaction scheme:

wherein A, Z¹, Z², Z³, n, Q¹ and B are as herein-defined, in the optionally presence of a catalytic or stoichiometric or excess amount, quantity of a base such as an inorganic and organic base. Preference is given to using alkali metal carbonates, such as sodium carbonate, potassium carbonate, potassium bicarbonate, sodium bicarbonate; heterocyclic aromatic bases, such as pyridine, picoline, lutidine, collidine; and also tertiary amines, such as trimethylamine, triethylamine, tributylamine, N,N-dimethylaniline, N,N-dimethylaminopyridine or N-methyl-piperidine.

Process P2 according to the invention is performed in the presence of a thionating agent.

Starting amide derivatives of formula (I) can be prepared according to processes P1.

Suitable thionating agents for carrying out process P2 according to the invention can be sulfur (S), sulfhydric acid (H₂S), sodium sulfide (Na₂S), sodium hydrosulfide (NaHS), boron trisulfide (B₂S₃), bis(diethylaluminium) sulfide ((AlEt₂)₂S), ammonium sulfide ((NH₄)₂S), phosphorous pentasulfide (P₂S₅), Lawesson's reagent (2,4-bis(4-methoxyphenyl)-1,2,3,4-dithiadiphosphetane 2,4-disulfide) or a polymer-supported thionating reagent such as described in Journal of the Chemical Society, Perkin 1 (2001), 358.

Work-up is carried out by customary methods. Generally, the reaction mixture is treated with water and the organic phase is separated off and, after drying, concentrated under reduced pressure. If appropriate, the remaining residue can, be freed by customary methods, such as chromatography, recrystallization or distillation, from any impurities that may still be present.

The compound according to the present invention can be prepared according to the general processes of preparation described above. It will nevertheless be understood that, on the basis of his general knowledge and of available publications, the skilled worker will be able to adapt this method according to the specifics of each of the compounds, which it is desired to synthesize.

In a further aspect, the present invention also relates to a fungicide composition comprising an effective and non-phytotoxic amount of an active compound of formula (I).

The expression “effective and non-phytotoxic amount” means an amount of composition according to the invention that is sufficient to control or destroy the fungi present or liable to appear on the crops and that does not entail any appreciable symptom of phytotoxicity for the said crops. Such an amount can vary within a wide range depending on the fungus to be controlled, the type of crop, the climatic conditions and the compounds included in the fungicide composition according to the invention. This amount can be determined by systematic field trials that are within the capabilities of a person skilled in the art.

Thus, according to the invention, there is provided a fungicide composition comprising, as an active ingredient, an effective amount of a compound of formula (I) as herein defined and an agriculturally acceptable support, carrier or filler.

According to the invention, the term “support” denotes a natural or synthetic, organic or inorganic compound with that the active compound of formula (I) is combined or associated to make it easier to apply, notably to the parts of the plant. This support is thus generally inert and should be agriculturally acceptable. The support can be a solid or a liquid. Examples of suitable supports include clays, natural or synthetic silicates, silica, resins, waxes, solid fertilisers, water, alcohols, in particular butanol, organic solvents, mineral and plant oils and derivatives thereof. Mixtures of such supports can also be used.

The composition according to the invention can also comprise additional components. In particular, the composition can further comprise a surfactant. The surfactant can be an emulsifier, a dispersing agent or a wetting agent of ionic or non-ionic type or a mixture of such surfactants. Mention can be made, for example, of polyacrylic acid salts, lignosulfonic acid salts, phenolsulfonic or naphthalenesulfonic acid salts, polycondensates of ethylene oxide with fatty alcohols or with fatty acids or with fatty amines, substituted phenols (in particular alkylphenols or arylphenols), salts of sulfosuccinic acid esters, taurine derivatives (in particular alkyl taurates), phosphoric esters of polyoxyethylated alcohols or phenols, fatty acid esters of polyols and derivatives of the above compounds containing sulfate, sulfonate and phosphate functions. The presence of at least one surfactant is generally essential when the active compound and/or the inert support are water-insoluble and when the vector agent for the application is water. Preferably, surfactant content can be comprised from 5% to 40% by weight of the composition.

Optionally, additional components can also be included, e.g. protective colloids, adhesives, thickeners, thixotropic agents, penetration agents, stabilisers, sequestering agents. More generally, the active compounds can be combined with any solid or liquid additive, that complies with the usual formulation techniques.

In general, the composition according to the invention can contain from 0.05 to 99% by weight of active compound, preferably 10 to 70% by weight.

Compositions according to the invention can be used in various forms such as aerosol dispenser, capsule suspension, cold fogging concentrate, dustable powder, emulsifiable concentrate, emulsion oil in water, emulsion water in oil, encapsulated granule, fine granule, flowable concentrate for seed treatment, gas (under pressure), gas generating product, granule, hot fogging concentrate, macrogranule, microgranule, oil dispersible powder, oil miscible flowable concentrate, oil miscible liquid, paste, plant rodlet, powder for dry seed treatment, seed coated with a pesticide, soluble concentrate, soluble powder, solution for seed treatment, suspension concentrate (flowable concentrate), ultra low volume (ULV) liquid, ultra low volume (ULV) suspension, water dispersible granules or tablets, water dispersible powder for slurry treatment, water soluble granules or tablets, water soluble powder for seed treatment and wettable powder. These compositions include not only compositions that are ready to be applied to the plant or seed to be treated by means of a suitable device, such as a spraying or dusting device, but also concentrated commercial compositions that must be diluted before application to the crop.

The compounds according to the invention can also be mixed with one or more insecticide, fungicide, bactericide, attractant, acaricide or pheromone active substance or other compounds with biological activity. The mixtures thus obtained have normally a broadened spectrum of activity. The mixtures with other fungicide compounds are particularly advantageous.

Examples of suitable fungicide mixing partners can be selected in the following lists:

(1) Inhibitors of the ergosterol biosynthesis, for example (1.1) aldimorph (1704-28-5), (1.2) azaconazole (60207-31-0), (1.3) bitertanol (55179-31-2), (1.4) bromuconazole (116255-48-2), (1.5) cyproconazole (113096-99-4), (1.6) diclobutrazole (75736-33-3), (1.7) difenoconazole (119446-68-3), (1.8) diniconazole (83657-24-3), (1.9) diniconazole-M (83657-18-5), (1.10) dodemorph (1593-77-7), (1.11) dodemorph acetate (31717-87-0), (1.12) epoxiconazole (106325-08-0), (1.13) etaconazole (60207-93-4), (1.14) fenarimol (60168-88-9), (1.15) fenbuconazole (114369-43-6), (1.16) fenhexamid (126833-17-8), (1.17) fenpropidin (67306-00-7), (1.18) fenpropimorph (67306-03-0), (1.19) fluquinconazole (136426-54-5), (1.20) flurprimidol (56425-91-3), (1.21) flusilazole (85509-19-9), (1.22) flutriafol (76674-21-0), (1.23) furconazole (112839-33-5), (1.24) furconazole-cis (112839-32-4), (1.25) hexaconazole (79983-71-4), (1.26) imazalil (60534-80-7), (1.27) imazalil sulfate (58594-72-2), (1.28) imibenconazole (86598-92-7), (1.29) ipconazole (125225-28-7), (1.30) metconazole (125116-23-6), (1.31) myclobutanil (88671-89-0), (1.32) naftifine (65472-88-0), (1.33) nuarimol (63284-71-9), (1.34) oxpoconazole (174212-12-5), (1.35) paclobutrazol (76738-62-0), (1.36) pefurazoate (101903-30-4), (1.37) penconazole (66246-88-6), (1.38) piperalin (3478-94-2), (1.39) prochloraz (67747-09-5), (1.40) propiconazole (60207-90-1), (1.41) prothioconazole (178928-70-6), (1.42) pyributicarb (88678-67-5), (1.43) pyrifenox (88283-41-4), (1.44) quinconazole (103970-75-8), (1.45) simeconazole (149508-90-7), (1.46) spiroxamine (118134-30-8), (1.47) tebuconazole (107534-96-3), (1.48) terbinafine (91161-71-6), (1.49) tetraconazole (112281-77-3), (1.50) triadimefon (43121-43-3), (1.51) triadimenol (89482-17-7), (1.52) tridemorph (81412-43-3), (1.53) triflumizole (68694-11-1), (1.54) triforine (26644-46-2), (1.55) triticonazole (131983-72-7), (1.56) uniconazole (83657-22-1), (1.57) uniconazole-p (83657-17-4), (1.58) viniconazole (77174-66-4), (1.59) voriconazole (137234-62-9), (1.60) 1-(4-chlorophenyl)-2-(1H-1,2,4-triazol-1-yl)cycloheptanol (129586-32-9), (1.61) methyl 1-(2,2-dimethyl-2,3-dihydro-1H-inden-1-yl)-1H-imidazole-5-carboxylate (110323-95-0), (1.62) N′-{5-(difluoromethyl)-2-methyl-4-[3-(trimethylsilyl)propoxy]phenyl}-N-ethyl-N-methylimidoformamide, (1.63) N-ethyl-N-methyl-N′-{2-methyl-5-(trifluoromethyl)-4-[3-(trimethylsilyl)propoxy]phenyl}imidoformamide and (1.64) O-[1-(4-methoxyphenoxy)-3,3-dimethylbutan-2-yl]1H-imidazole-1-carbothioate (111226-71-2). (2) inhibitors of the respiratory chain at complex I or II, for example (2.1) bixafen (581809-46-3), (2.2) boscalid (188425-85-6), (2.3) carboxin (5234-68-4), (2.4) diflumetorim (130339-07-0), (2.5) fenfuram (24691-80-3), (2.6) fluopyram (658066-35-4), (2.7) flutolanil (66332-96-5), (2.8) fluxapyroxad (907204-31-3), (2.9) furametpyr (123572-88-3), (2.10) furmecyclox (60568-05-0), (2.11) isopyrazam (mixture of syn-racemate 1RS,4SR,9RS and anti-epimeric racemate 1RS,4SR,9SR) (881685-58-1), (2.12) isopyrazam (anti-epimeric racemate 1RS,4SR,9SR), (2.13) isopyrazam (anti-epimeric enantiomer 1R,4S,9S), (2.14) isopyrazam (anti-epimeric enantiomer 1S,4R,9R), (2.15) isopyrazam (syn epimeric racemate 1RS,4SR,9RS), (2.16) isopyrazam (syn-epimeric enantiomer 1R,4S,9R), (2.17) isopyrazam (syn-epimeric enantiomer 1S,4R,9S), (2.18) mepronil (55814-41-0), (2.19) oxycarboxin (5259-88-1), (2.20) penflufen (494793-67-8), (2.21) penthiopyrad (183675-82-3), (2.22) sedaxane (874967-67-6), (2.23) thifluzamide (130000-40-7), (2.24) 1-methyl-N-[2-(1,1,2,2-tetrafluoroethoxy)phenyl]-3-(trifluoromethyl)-1H-pyrazole-4-carboxamide, (2.25) 3-(difluoromethyl)-1-methyl-N-[2-(1,1,2,2-tetrafluoroethoxy)phenyl]-1H-pyrazole-4-carboxamide, (2.26) 3-(difluoromethyl)-N-[4-fluoro-2-(1,1,2,3,3,3-hexafluoropropoxy)phenyl]-1-methyl-1H-pyrazole-4-carboxamide, (2.27) N-[1-(2,4-dichlorophenyl)-1-methoxypropan-2-yl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide (1092400-95-7) (WO 2008148570), (2.28) 5,8-difluoro-N-[2-(2-fluoro-4-{[4-(trifluoromethyl)pyridin-2-yl]oxy}phenyl)ethyl]quinazolin-4-amine (1210070-84-0) (WO2010025451), (2.29) N-[9-(dichloromethylene)-1,2,3,4-tetrahydro-1,4-methanonaphthalen-5-yl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide, (2.30) N-[(1S,4R)-9-(dichloromethylene)-1,2,3,4-tetrahydro-1,4-methanonaphthalen-5-yl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide and (2.31) N-[(1R,4S)-9-(dichloromethylene)-1,2,3,4-tetrahydro-1,4-methanonaphthalen-5-yl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide. (3) inhibitors of the respiratory chain at complex III, for example (3.1) ametoctradin (865318-97-4), (3.2) amisulbrom (348635-87-0), (3.3) azoxystrobin (131860-33-8), (3.4) cyazofamid (120116-88-3), (3.5) coumethoxystrobin (850881-30-0), (3.6) coumoxystrobin (850881-70-8), (3.7) dimoxystrobin (141600-52-4), (3.8) enestroburin (238410-11-2) (WO 2004/058723), (3.9) famoxadone (131807-57-3) (WO 2004/058723), (3.10) fenamidone (161326-34-7) (WO 2004/058723), (3.11) fenoxystrobin (918162-02-4), (3.12) fluoxastrobin (361377-29-9) (WO 2004/058723), (3.13) kresoxim-methyl (143390-89-0) (WO 2004/058723), (3.14) metominostrobin (133408-50-1) (WO 2004/058723), (3.15) orysastrobin (189892-69-1) (WO 2004/058723), (3.16) picoxystrobin (117428-22-5) (WO 2004/058723), (3.17) pyraclostrobin (175013-18-0) (WO 2004/058723), (3.18) pyrametostrobin (915410-70-7) (WO 2004/058723), (3.19) pyraoxystrobin (862588-11-2) (WO 2004/058723), (3.20) pyribencarb (799247-52-2) (WO 2004/058723), (3.21) triclopyricarb (902760-40-1), (3.22) trifloxystrobin (141517-21-7) (WO 2004/058723), (3.23) (2E)-2-(2-{[6-(3-chloro-2-methylphenoxy)-5-fluoropyrimidin-4-yl]oxy}phenyl)-2-(methoxyimino)-N-methylethanamide (WO 2004/058723), (3.24) (2E)-2-(methoxyimino)-N-methyl-2-(2-{[({(1E)-1-[3-(trifluoromethyl)phenyl]ethylidene}amino)oxy]methyl}phenyl)ethanamide (WO 2004/058723), (3.25) (2E)-2-(methoxyimino)-N-methyl-2-{2-[(E)-({1-[3-(trifluoromethyl)phenyl]ethoxy}imino)methyl]phenyl}ethanamide (158169-73-4), (3.26) (2E)-2-{2-[({[(1E)-1-(3-{[(E)-1-fluoro-2-phenylethenyl]oxy}phenyl)ethylidene]amino}oxy)methyl]phenyl}-2-(methoxyimino)-N-methylethanamide (326896-28-0), (3.27) (2E)-2-{2-[({[(2E,3E)-4-(2,6-dichlorophenyl)but-3-en-2-ylidene]amino}oxy)methyl]phenyl}-2-(methoxyimino)-N-methylethanamide, (3.28) 2-chloro-N-(1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl)pyridine-3-carboxamide (119899-14-8), (3.29) 5-methoxy-2-methyl-4-(2-{[({(1E)-1-[3-(trifluoromethyl)phenyl]ethylidene}amino)oxy]methyl}phenyl)-2,4-dihydro-3H-1,2,4-triazol-3-one, (3.30) methyl (2E)-2-{2-[({cyclopropyl[(4-methoxyphenyl)imino]methyl}sulfanyl)methyl]phenyl}-3-methoxprop-2-enoate (149601-03-6), (3.31) N-(3-ethyl-3,5,5-trimethylcyclohexyl)-3-(formylamino)-2-hydroxybenzamide (226551-21-9), (3.32) 2-{2-[(2,5-dimethylphenoxy)methyl]phenyl}-2-methoxy-N-methylacetamide (173662-97-0) and (3.33) (2R)-2-{2-[(2,5-dimethylphenoxy)methyl]phenyl}-2-methoxy-N-methylacetamide (394657-24-0). (4) Inhibitors of the mitosis and cell division, for example (4.1) benomyl (17804-35-2), (4.2) carbendazim (10605-21-7), (4.3) chlorfenazole (3574-96-7), (4.4) diethofencarb (87130-20-9), (4.5) ethaboxam (162650-77-3), (4.6) fluopicolide (239110-15-7), (4.7) fuberidazole (3878-19-1), (4.8) pencycuron (66063-05-6), (4.9) thiabendazole (148-79-8), (4.10) thiophanate-methyl (23564-05-8), (4.11) thiophanate (23564-06-9), (4.12) zoxamide (156052-68-5), (4.13) 5-chloro-7-(4-methylpiperidin-1-yl)-6-(2,4,6-trifluorophenyl)[1,2,4]triazolo[1,5-a]pyrimidine (214706-53-3) and (4.14) 3-chloro-5-(6-chloropyridin-3-yl)-6-methyl-4-(2,4,6-trifluorophenyl)pyridazine (1002756-87-7). (5) Compounds capable to have a multisite action, like for example (5.1) bordeaux mixture (8011-63-0), (5.2) captafol (2425-06-1), (5.3) captan (133-06-2) (WO 02/12172), (5.4) chlorothalonil (1897-45-6), (5.5) copper hydroxide (20427-59-2), (5.6) copper naphthenate (1338-02-9), (5.7) copper oxide (1317-39-1), (5.8) copper oxychloride (1332-40-7), (5.9) copper (2+) sulfate (7758-98-7), (5.10) dichlofluanid (1085-98-9), (5.11) dithianon (3347-22-6), (5.12) dodine (2439-10-3), (5.13) dodine free base, (5.14) ferbam (14484-64-1), (5.15) fluorofolpet (719-96-0), (5.16) folpet (133-07-3), (5.17) guazatine (108173-90-6), (5.18) guazatine acetate, (5.19) iminoctadine (13516-27-3), (5.20) iminoctadine albesilate (169202-06-6), (5.21) iminoctadine triacetate (57520-17-9), (5.22) mancopper (53988-93-5), (5.23) mancozeb (8018-01-7), (5.24) maneb (12427-38-2), (5.25) metiram (9006-42-2), (5.26) metiram zinc (9006-42-2), (5.27) oxine-copper (10380-28-6), (5.28) propamidine (104-32-5), (5.29) propineb (12071-83-9), (5.30) sulfur and sulfur preparations including calcium polysulfide (7704-34-9), (5.31) thiram (137-26-8), (5.32) tolylfluanid (731-27-1), (5.33) zineb (12122-67-7) and (5.34) ziram (137-30-4). (6) Compounds capable to induce a host defence, for example (6.1) acibenzolar-5-methyl (135158-54-2), (6.2) isotianil (224049-04-1), (6.3) probenazole (27605-76-1) and (6.4) tiadinil (223580-51-6). (7) Inhibitors of the amino acid and/or protein biosynthesis, for example (7.1) andoprim (23951-85-1), (7.2) blasticidin-S (2079-00-7), (7.3) cyprodinil (121552-61-2), (7.4) kasugamycin (6980-18-3), (7.5) kasugamycin hydrochloride hydrate (19408-46-9), (7.6) mepanipyrim (110235-47-7), (7.7) pyrimethanil (53112-28-0) and (7.8) 3-(5-fluoro-3,3,4,4-tetramethyl-3,4-dihydroisoquinolin-1-yl)quinoline (861647-32-7) (WO2005070917). (8) Inhibitors of the ATP production, for example (8.1) fentin acetate (900-95-8), (8.2) fentin chloride (639-58-7), (8.3) fentin hydroxide (76-87-9) and (8.4) silthiofam (175217-20-6). (9) Inhibitors of the cell wall synthesis, for example (9.1) benthiavalicarb (177406-68-7), (9.2) dimethomorph (110488-70-5), (9.3) flumorph (211867-47-9), (9.4) iprovalicarb (140923-17-7), (9.5) mandipropamid (374726-62-2), (9.6) polyoxins (11113-80-7), (9.7) polyoxorim (22976-86-9), (9.8) validamycin A (37248-47-8) and (9.9) valifenalate (283159-94-4; 283159-90-0). (10) Inhibitors of the lipid and membrane synthesis, for example (10.1) biphenyl (92-52-4), (10.2) chloroneb (2675-77-6), (10.3) dicloran (99-30-9), (10.4) edifenphos (17109-49-8), (10.5) etridiazole (2593-15-9), (10.6) iodocarb (55406-53-6), (10.7) iprobenfos (26087-47-8), (10.8) isoprothiolane (50512-35-1), (10.9) propamocarb (25606-41-1), (10.10) propamocarb hydrochloride (25606-41-1), (10.11) prothiocarb (19622-08-3), (10.12) pyrazophos (13457-18-6), (10.13) quintozene (82-68-8), (10.14) tecnazene (117-18-0) and (10.15) tolclofos-methyl (57018-04-9). (11) Inhibitors of the melanine biosynthesis, for example (11.1) carpropamid (104030-54-8), (11.2) diclocymet (139920-32-4), (11.3) fenoxanil (115852-48-7), (11.4) phthalide (27355-22-2), (11.5) pyroquilon (57369-32-1), (11.6) tricyclazole (41814-78-2) and (11.7) 2,2,2-trifluoroethyl {3-methyl-1-[(4-methylbenzoyl)amino]butan-2-yl}carbamate (851524-22-6) (WO2005042474). (12) Inhibitors of the nucleic acid synthesis, for example (12.1) benalaxyl (71626-11-4), (12.2) benalaxyl-M (kiralaxyl) (98243-83-5), (12.3) bupirimate (41483-43-6), (12.4) clozylacon (67932-85-8), (12.5) dimethirimol (5221-53-4), (12.6) ethirimol (23947-60-6), (12.7) furalaxyl (57646-30-7), (12.8) hymexazol (10004-44-1), (12.9) metalaxyl (57837-19-1), (12.10) metalaxyl-M (mefenoxam) (70630-17-0), (12.11) ofurace (58810-48-3), (12.12) oxadixyl (77732-09-3) and (12.13) oxolinic acid (14698-29-4). (13) Inhibitors of the signal transduction, for example (13.1) chlozolinate (84332-86-5), (13.2) fenpiclonil (74738-17-3), (13.3) fludioxonil (131341-86-1), (13.4) iprodione (36734-19-7), (13.5) procymidone (32809-16-8), (13.6) quinoxyfen (124495-18-7) and (13.7) vinclozolin (50471-44-8). (14) Compounds capable to act as an uncoupler, for example (14.1) binapacryl (485-31-4), (14.2) dinocap (131-72-6), (14.3) ferimzone (89269-64-7), (14.4) fluazinam (79622-59-6) and (14.5) meptyldinocap (131-72-6). (15) Further compounds, for example (15.1) benthiazole (21564-17-0), (15.2) bethoxazin (163269-30-5), (15.3) capsimycin (70694-08-5), (15.4) carvone (99-49-0), (15.5) chinomethionat (2439-01-2), (15.6) pyriofenone (chlazafenone) (688046-61-9), (15.7) cufraneb (11096-18-7), (15.8) cyflufenamid (180409-60-3), (15.9) cymoxanil (57966-95-7), (15.10) cyprosulfamide (221667-31-8), (15.11) dazomet (533-74-4), (15.12) debacarb (62732-91-6), (15.13) dichlorophen (97-23-4), (15.14) diclomezine (62865-36-5), (15.15) difenzoquat (49866-87-7), (15.16) difenzoquat methylsulfate (43222-48-6), (15.17) diphenylamine (122-39-4), (15.18) ecomate, (15.19) fenpyrazamine (473798-59-3), (15.20) flumetover (154025-04-4), (15.21) fluoroimide (41205-21-4), (15.22) flusulfamide (106917-52-6), (15.23) flutianil (304900-25-2), (15.24) fosetyl-aluminium (39148-24-8), (15.25) fosetyl-calcium, (15.26) fosetyl-sodium (39148-16-8), (15.27) hexachlorobenzene (118-74-1), (15.28) irumamycin (81604-73-1), (15.29) methasulfocarb (66952-49-6), (15.30) methyl isothiocyanate (556-61-6), (15.31) metrafenone (220899-03-6), (15.32) mildiomycin (67527-71-3), (15.33) natamycin (7681-93-8), (15.34) nickel dimethyldithiocarbamate (15521-65-0), (15.35) nitrothal-isopropyl (10552-74-6), (15.36) octhilinone (26530-20-1), (15.37) oxamocarb (917242-12-7), (15.38) oxyfenthiin (34407-87-9), (15.39) pentachlorophenol and salts (87-86-5), (15.40) phenothrin, (15.41) phosphorous acid and its salts (13598-36-2), (15.42) propamocarb-fosetylate, (15.43) propanosine-sodium (88498-02-6), (15.44) proquinazid (189278-12-4), (15.45) pyrimorph (868390-90-3), (15.45e) (2E)-3-(4-tert-butylphenyl)-3-(2-chloropyridin-4-yl)-1-(morpholin-4-yl)prop-2-en-1-one (1231776-28-5), (15.45z) (2Z)-3-(4-tert-butylphenyl)-3-(2-chloropyridin-4-yl)-1-(morpholin-4-yl)prop-2-en-1-one (1231776-29-6), (15.46) pyrrolnitrine (1018-71-9) (EP-A 1 559 320), (15.47) tebufloquin (376645-78-2), (15.48) tecloftalam (76280-91-6), (15.49) tolnifanide (304911-98-6), (15.50) triazoxide (72459-58-6), (15.51) trichlamide (70193-21-4), (15.52) zarilamid (84527-51-5), (15.53) (3S,6S,7R,8R)-8-benzyl-3-[({3-[(isobutyryloxy)methoxy]-4-methoxypyridin-2-yl}carbonyl)amino]-6-methyl-4,9-dioxo-1,5-dioxonan-7-yl 2-methylpropanoate (517875-34-2) (WO2003035617), (15.54) 1-(4-{4-[(5R)-5-(2,6-difluorophenyl)-4,5-dihydro-1,2-oxazol-3-yl]-1,3-thiazol-2-yl}piperidin-1-yl)-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]ethanone (1003319-79-6) (WO 2008013622), (15.55) 1-(4-{4-[(5S)-5-(2,6-difluorophenyl)-4,5-dihydro-1,2-oxazol-3-yl]-1,3-thiazol-2-yl}piperidin-1-yl)-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]ethanone (1003319-80-9) (WO 2008013622), (15.56) 1-(4-{4-[5-(2,6-difluorophenyl)-4,5-dihydro-1,2-oxazol-3-yl]-1,3-thiazol-2-yl}piperidin-1-yl)-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]ethanone (1003318-67-9) (WO 2008013622), (15.57) 1-(4-methoxyphenoxy)-3,3-dimethylbutan-2-yl 1H-imidazole-1-carboxylate (111227-17-9), (15.58) 2,3,5,6-tetrachloro-4-(methylsulfonyl)pyridine (13108-52-6), (15.59) 2,3-dibutyl-6-chlorothieno[2,3-d]pyrimidin-4(3H)-one (221451-58-7), (15.60) 2,6-dimethyl-1H,5H-[1,4]dithiino[2,3-c:5,6-c′]dipyrrole-1,3,5,7(2H,6H)-tetrone, (15.61) 2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]-1-(4-{4-[(5R)-5-phenyl-4,5-dihydro-1,2-oxazol-3-yl]-1,3-thiazol-2-yl}piperidin-1-yl)ethanone (1003316-53-7) (WO 2008013622), (15.62) 2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]-1-(4-{4-[(5S)-5-phenyl-4,5-dihydro-1,2-oxazol-3-yl]-1,3-thiazol-2-yl}piperidin-1-yl)ethanone (1003316-54-8) (WO 2008013622), (15.63) 2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]-1-{4-[4-(5-phenyl-4,5-dihydro-1,2-oxazol-3-yl)-1,3-thiazol-2-yl]piperidin-1-yl}ethanone (1003316-51-5) (WO 2008013622), (15.64) 2-butoxy-6-iodo-3-propyl-4H-chromen-4-one, (15.65) 2-chloro-5-[2-chloro-1-(2,6-difluoro-4-methoxyphenyl)-4-methyl-1H-imidazol-5-yl]pyridine, (15.66) 2-phenylphenol and salts (90-43-7), (15.67) 3-(4,4,5-trifluoro-3,3-dimethyl-3,4-dihydroisoquinolin-1-yl)quinoline (861647-85-0) (WO2005070917), (15.68) 3,4,5-trichloropyridine-2,6-dicarbonitrile (17824-85-0), (15.69) 3-[5-(4-chlorophenyl)-2,3-dimethyl-1,2-oxazolidin-3-yl]pyridine, (15.70) 3-chloro-5-(4-chlorophenyl)-4-(2,6-difluorophenyl)-6-methylpyridazine, (15.71) 4-(4-chlorophenyl)-5-(2,6-difluorophenyl)-3,6-dimethylpyridazine, (15.72) 5-amino-1,3,4-thiadiazole-2-thiol, (15.73) 5-chloro-N′-phenyl-N′-(prop-2-yn-1-yl)thiophene-2-sulfonohydrazide (134-31-6), (15.74) 5-fluoro-2-[(4-fluorobenzyl)oxy]pyrimidin-4-amine (1174376-11-4) (WO2009094442), (15.75) 5-fluoro-2-[(4-methylbenzyl)oxy]pyrimidin-4-amine (1174376-25-0) (WO2009094442), (15.76) 5-methyl-6-octyl[1,2,4]triazolo[1,5-a]pyrimidin-7-amine, (15.77) ethyl (2Z)-3-amino-2-cyano-3-phenylprop-2-enoate, (15.78) N′-(4-{[3-(4-chlorobenzyl)-1,2,4-thiadiazol-5-yl]oxy}-2,5-dimethylphenyl)-N-ethyl-N-methylimidoformamide, (15.79) N-(4-chlorobenzyl)-3-[3-methoxy-4-(prop-2-yn-1-yloxy)phenyl]propanamide, (15.80) N-[(4-chlorophenyl)(cyano)methyl]-3-[3-methoxy-4-(prop-2-yn-1-yloxy)phenyl]propanamide, (15.81) N-[(5-bromo-3-chloropyridin-2-yl)methyl]-2,4-dichloropyridine-3-carboxamide, (15.82) N-[1-(5-bromo-3-chloropyridin-2-yl)ethyl]-2,4-dichloropyridine-3-carboxamide, (15.83) N-[1-(5-bromo-3-chloropyridin-2-yl)ethyl]-2-fluoro-4-iodopyridine-3-carboxamide, (15.84) N-{(E)-[(cyclopropylmethoxy)imino][6-(difluoromethoxy)-2,3-difluorophenyl]methyl}-2-phenylacetamide (221201-92-9), (15.85) N-{(Z)-[(cyclopropylmethoxy)imino][6-(difluoromethoxy)-2,3-difluorophenyl]methyl}-2-phenylacetamide (221201-92-9), (15.86) N′-{4-[(3-tert-butyl-4-cyano-1,2-thiazol-5-yl)oxy]-2-chloro-5-methylphenyl}-N-ethyl-N-methylimidoformamide, (15.87) N-methyl-2-(1-{[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-N-(1,2,3,4-tetrahydronaphthalen-1-yl)-1,3-thiazole-4-carboxamide (922514-49-6) (WO 2007014290), (15.88) N-methyl-2-(1-{[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-N-[(1R)-1,2,3,4-tetrahydronaphthalen-1-yl]-1,3-thiazole-4-carboxamide (922514-07-6) (WO 2007014290), (15.89) N-methyl-2-(1-{[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-N-[(1S)-1,2,3,4-tetrahydronaphthalen-1-yl]-1,3-thiazole-4-carboxamide (922514-48-5) (WO 2007014290), (15.90) pentyl {6-[({[(1-methyl-1H-tetrazol-5-yl)(phenyl)methylidene]amino}oxy)methyl]pyridin-2-yl}carbamate, (15.91) phenazine-1-carboxylic acid, (15.92) quinolin-8-ol (134-31-6), (15.93) quinolin-8-ol sulfate (2:1) (134-31-6) and (15.94) tert-butyl {6-[({[(1-methyl-1H-tetrazol-5-yl)(phenyl)methylene]amino}oxy)methyl]pyridin-2-yl}carbamate. (16) Further compounds, for example (16.1) 1-methyl-3-(trifluoromethyl)-N-[2′-(trifluoromethyl)biphenyl-2-yl]-1H-pyrazole-4-carboxamide, (16.2) N-(4′-chlorobiphenyl-2-yl)-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide, (16.3) N-(2′,4′-dichlorobiphenyl-2-yl)-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide, (16.4) 3-(difluoromethyl)-1-methyl-N-[4′-(trifluoromethyl)biphenyl-2-yl]-1H-pyrazole-4-carboxamide, (16.5) N-(2′,5′-difluorobiphenyl-2-yl)-1-methyl-3-(trifluoromethyl)-1H-pyrazole-4-carboxamide, (16.6) 3-(difluoromethyl)-1-methyl-N-[4′-(prop-1-yn-1-yl)biphenyl-2-yl]-1H-pyrazole-4-carboxamide (known from WO 2004/058723), (16.7) 5-fluoro-1,3-dimethyl-N-[4′-(prop-1-yn-1-yl)biphenyl-2-yl]-1H-pyrazole-4-carboxamide (known from WO 2004/058723), (16.8) 2-chloro-N-[4′-(prop-1-yn-1-yl)biphenyl-2-yl]pyridine-3-carboxamide (known from WO 2004/058723), (16.9) 3-(difluoromethyl)-N-[4′-(3,3-dimethylbut-1-yn-1-yl)biphenyl-2-yl]-1-methyl-1H-pyrazole-4-carboxamide (known from WO 2004/058723), (16.10) N-[4′-(3,3-dimethylbut-1-yn-1-yl)biphenyl-2-yl]-5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide (known from WO 2004/058723), (16.11) 3-(difluoromethyl)-N-(4′-ethynylbiphenyl-2-yl)-1-methyl-1H-pyrazole-4-carboxamide (known from WO 2004/058723), (16.12) N-(4′-ethynylbiphenyl-2-yl)-5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide (known from WO 2004/058723), (16.13) 2-chloro-N-(4′-ethynylbiphenyl-2-yl)pyridine-3-carboxamide (known from WO 2004/058723), (16.14) 2-chloro-N-[4′-(3,3-dimethylbut-1-yn-1-yl)biphenyl-2-yl]pyridine-3-carboxamide (known from WO 2004/058723), (16.15) 4-(difluoromethyl)-2-methyl-N-[4′-(trifluoromethyl)biphenyl-2-yl]-1,3-thiazole-5-carboxamide (known from WO 2004/058723), (16.16) 5-fluoro-N-[4′-(3-hydroxy-3-methylbut-1-yn-1-yl)biphenyl-2-yl]-1,3-dimethyl-1H-pyrazole-4-carboxamide (known from WO 2004/058723), (16.17) 2-chloro-N-[4′-(3-hydroxy-3-methylbut-1-yn-1-yl)biphenyl-2-yl]pyridine-3-carboxamide (known from WO 2004/058723), (16.18) 3-(difluoromethyl)-N-[4′-(3-methoxy-3-methylbut-1-yn-1-yl)biphenyl-2-yl]-1-methyl-1H-pyrazole-4-carboxamide (known from WO 2004/058723), (16.19) 5-fluoro-N-[4′-(3-methoxy-3-methylbut-1-yn-1-yl)biphenyl-2-yl]-1,3-dimethyl-1H-pyrazole-4-carboxamide (known from WO 2004/058723), (16.20) 2-chloro-N-[4′-(3-methoxy-3-methylbut-1-yn-1-yl)biphenyl-2-yl]pyridine-3-carboxamide (known from WO 2004/058723), (16.21) (5-bromo-2-methoxy-4-methylpyridin-3-yl)(2,3,4-trimethoxy-6-methylphenyl)methanone (known from EP-A 1 559 320), (16.22) N-[2-(4-{[3-(4-chlorophenyl)prop-2-yn-1-yl]oxy}-3-methoxyphenyl)ethyl]-N2-(methylsulfonyl)valinamide (220706-93-4), (16.23) 4-oxo-4-[(2-phenylethyl)amino]butanoic acid and (16.24) but-3-yn-1-yl {6-[({[(Z)-(1-methyl-1H-tetrazol-5-yl)(phenyl)methylene]amino}oxy)methyl]pyridin-2-yl}carbamate.

All named mixing partners of the classes (1) to (16) can, if their functional groups enable this, optionally form salts with suitable bases or acids.

The composition according to the invention comprising a mixture of a compound of formula (I) with a bactericide compound can also be particularly advantageous. Examples of suitable bactericide mixing partners can be selected in the following list: bronopol, dichlorophen, nitrapyrin, nickel dimethyldithiocarbamate, kasugamycin, octhilinone, furancarboxylic acid, oxytetracycline, probenazole, streptomycin, tecloftalam, copper sulfate and other copper preparations.

The compounds of formula (I) and the fungicide composition according to the invention can be used to curatively or preventively control the phytopathogenic fungi of plants or crops.

Thus, according to a further aspect of the invention, there is provided a method for curatively or preventively controlling the phytopathogenic fungi of plants or crops characterised in that a compound of formula (I) or a fungicide composition according to the invention is applied to the seed, the plant or to the fruit of the plant or to the soil wherein the plant is growing or wherein it is desired to grow.

The method of treatment according to the invention can also be useful to treat propagation material such as tubers or rhizomes, but also seeds, seedlings or seedlings pricking out and plants or plants pricking out. This method of treatment can also be useful to treat roots. The method of treatment according to the invention can also be useful to treat the overground parts of the plant such as trunks, stems or stalks, leaves, flowers and fruit of the concerned plant.

According to the invention all plants and plant parts can be treated. By plants is meant all plants and plant populations such as desirable and undesirable wild plants, cultivars and plant varieties (whether or not protectable by plant variety or plant breeder's rights). Cultivars and plant varieties can be plants obtained by conventional propagation and breeding methods which can be assisted or supplemented by one or more biotechnological methods such as by use of double haploids, protoplast fusion, random and directed mutagenesis, molecular or genetic markers or by bioengineering and genetic engineering methods. By plant parts is meant all above ground and below ground parts and organs of plants such as shoot, leaf, blossom and root, whereby for example leaves, needles, stems, branches, blossoms, fruiting bodies, fruits and seed as well as roots, corms and rhizomes are listed. Crops and vegetative and generative propagating material, for example cuttings, corms, rhizomes, runners and seeds also belong to plant parts.

Among the plants that can be protected by the method according to the invention, mention may be made of major field crops like corn, soybean, cotton, Brassica oilseeds such as Brassica napus (e.g. canola), Brassica rapa, B. juncea (e.g. mustard) and Brassica carinata, rice, wheat, sugarbeet, sugarcane, oats, rye, barley, millet, triticale, flax, vine and various fruits and vegetables of various botanical taxa such as Rosaceae sp. (for instance pip fruit such as apples and pears, but also stone fruit such as apricots, cherries, almonds and peaches, berry fruits such as strawberries), Ribesioidae sp., Juglandaceae sp., Betulaceae sp., Anacardiaceae sp., Fagaceae sp., Moraceae sp., Oleaceae sp., Actimidaceae sp., Lauraceae sp., Musaceae sp. (for instance banana trees and plantings), Rubiaceae sp. (for instance coffee), Theaceae sp., Sterculiceae sp., Rutaceae sp. (for instance lemons, oranges and grapefruit); Solanaceae sp. (for instance tomatoes, potatoes, peppers, eggplant), Liliaceae sp., Compositiae sp. (for instance lettuce, artichoke and chicory—including root chicory, endive or common chicory), Umbelliferae sp. (for instance carrot, parsley, celery and celeriac), Cucurbitaceae sp. (for instance cucumber—including pickling cucumber, squash, watermelon, gourds and melons), Alliaceae sp. (for instance onions and leek), Cruciferae sp. (for instance white cabbage, red cabbage, broccoli, cauliflower, brussel sprouts, pak choi, kohlrabi, radish, horseradish, cress, Chinese cabbage), Leguminosae sp. (for instance peanuts, peas and beans beans—such as climbing beans and broad beans), Chenopodiaceae sp. (for instance mangold, spinach beet, spinach, beetroots), Malvaceae (for instance okra), Asparagaceae (for instance asparagus); horticultural and forest crops; ornamental plants; as well as genetically modified homologues of these crops.

The method of treatment according to the invention can be used in the treatment of genetically modified organisms (GMOs), e.g. plants or seeds. Genetically modified plants (or transgenic plants) are plants of which a heterologous gene has been stably integrated into genome. The expression “heterologous gene” essentially means a gene which is provided or assembled outside the plant and when introduced in the nuclear, chloroplastic or mitochondrial genome gives the transformed plant new or improved agronomic or other properties by expressing a protein or polypeptide of interest or by downregulating or silencing other gene(s) which are present in the plant (using for example, antisense technology, cosuppression technology or RNA interference—RNAi—technology). A heterologous gene that is located in the genome is also called a transgene. A transgene that is defined by its particular location in the plant genome is called a transformation or transgenic event.

Depending on the plant species or plant cultivars, their location and growth conditions (soils, climate, vegetation period, diet), the treatment according to the invention may also result in additional effects. Thus, for example, reduced application rates and/or a widening of the activity spectrum and/or an increase in the activity of the active compounds and compositions which can be used according to the invention, better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or to water or soil salt content, increased flowering performance, easier harvesting, accelerated maturation, higher harvest yields, bigger fruits, larger plant height, greener leaf color, earlier flowering, higher quality and/or a higher nutritional value of the harvested products, higher sugar concentration within the fruits, better storage stability and/or processability of the harvested products are possible, which exceed the effects which were actually to be expected.

At certain application rates, the active compound combinations according to the invention may also have a strengthening effect in plants. Accordingly, they are also suitable for mobilizing the defense system of the plant against attack by unwanted microorganisms. This may, if appropriate, be one of the reasons of the enhanced activity of the combinations according to the invention, for example against fungi. Plant-strengthening (resistance-inducing) substances are to be understood as meaning, in the present context, those substances or combinations of substances which are capable of stimulating the defense system of plants in such a way that, when subsequently inoculated with unwanted microorganisms, the treated plants display a substantial degree of resistance to these microorganisms. In the present case, unwanted microorganisms are to be understood as meaning phytopathogenic fungi, bacteria and viruses. Thus, the substances according to the invention can be employed for protecting plants against attack by the abovementioned pathogens within a certain period of time after the treatment. The period of time within which protection is effected generally extends from 1 to 10 days, preferably 1 to 7 days, after the treatment of the plants with the active compounds.

Plants and plant cultivars which are preferably to be treated according to the invention include all plants which have genetic material which impart particularly advantageous, useful traits to these plants (whether obtained by breeding and/or biotechnological means).

Plants and plant cultivars which are also preferably to be treated according to the invention are resistant against one or more biotic stresses, i.e. said plants show a better defense against animal and microbial pests, such as against nematodes, insects, mites, phytopathogenic fungi, bacteria, viruses and/or viroids.

Examples of nematode resistant plants are described in e.g. U.S. patent application Ser. Nos. 11/765,491, 11/765,494, 10/926,819, 10/782,020, 12/032,479, 10/783,417, 10/782,096, 11/657,964, 12/192,904, 11/396,808, 12/166,253, 12/166,239, 12/166,124, 12/166,209, 11/762,886, 12/364,335, 11/763,947, 12/252,453, 12/209,354, 12/491,396 or 12/497,221.

Plants and plant cultivars which may also be treated according to the invention are those plants which are resistant to one or more abiotic stresses. Abiotic stress conditions may include, for example, drought, cold temperature exposure, heat exposure, osmotic stress, flooding, increased soil salinity, increased mineral exposure, ozone exposure, high light exposure, limited availability of nitrogen nutrients, limited availability of phosphorus nutrients, shade avoidance.

Plants and plant cultivars which may also be treated according to the invention, are those plants characterized by enhanced yield characteristics. Increased yield in said plants can be the result of, for example, improved plant physiology, growth and development, such as water use efficiency, water retention efficiency, improved nitrogen use, enhanced carbon assimilation, improved photosynthesis, increased germination efficiency and accelerated maturation. Yield can furthermore be affected by improved plant architecture (under stress and non-stress conditions), including but not limited to, early flowering, flowering control for hybrid seed production, seedling vigor, plant size, internode number and distance, root growth, seed size, fruit size, pod size, pod or ear number, seed number per pod or ear, seed mass, enhanced seed filling, reduced seed dispersal, reduced pod dehiscence and lodging resistance. Further yield traits include seed composition, such as carbohydrate content, protein content, oil content and composition, nutritional value, reduction in anti-nutritional compounds, improved processability and better storage stability.

Examples of plants with the above-mentioned traits are non-exhaustively listed in Table A.

Plants that may be treated according to the invention are hybrid plants that already express the characteristic of heterosis or hybrid vigor which results in generally higher yield, vigor, health and resistance towards biotic and abiotic stresses). Such plants are typically made by crossing an inbred male-sterile parent line (the female parent) with another inbred male-fertile parent line (the male parent). Hybrid seed is typically harvested from the male sterile plants and sold to growers. Male sterile plants can sometimes (e.g. in corn) be produced by detasseling, i.e. the mechanical removal of the male reproductive organs (or males flowers) but, more typically, male sterility is the result of genetic determinants in the plant genome. In that case, and especially when seed is the desired product to be harvested from the hybrid plants it is typically useful to ensure that male fertility in the hybrid plants is fully restored. This can be accomplished by ensuring that the male parents have appropriate fertility restorer genes which are capable of restoring the male fertility in hybrid plants that contain the genetic determinants responsible for male-sterility. Genetic determinants for male sterility may be located in the cytoplasm. Examples of cytoplasmic male sterility (CMS) were for instance described in Brassica species (WO 92/05251, WO 95/09910, WO 98/27806, WO 05/002324, WO 06/021972 and U.S. Pat. No. 6,229,072). However, genetic determinants for male sterility can also be located in the nuclear genome. Male sterile plants can also be obtained by plant biotechnology methods such as genetic engineering. A particularly useful means of obtaining male-sterile plants is described in WO 89/10396 in which, for example, a ribonuclease such as barnase is selectively expressed in the tapetum cells in the stamens. Fertility can then be restored by expression in the tapetum cells of a ribonuclease inhibitor such as barstar (e.g. WO 91/02069).

Plants or plant cultivars (obtained by plant biotechnology methods such as genetic engineering) which may be treated according to the invention are herbicide-tolerant plants, i.e. plants made tolerant to one or more given herbicides. Such plants can be obtained either by genetic transformation, or by selection of plants containing a mutation imparting such herbicide tolerance.

Herbicide-resistant plants are for example glyphosate-tolerant plants, i.e. plants made tolerant to the herbicide glyphosate or salts thereof. Plants can be made tolerant to glyphosate through different means. For example, glyphosate-tolerant plants can be obtained by transforming the plant with a gene encoding the enzyme 5-enolpyruvylshikimate-3-phosphate synthase (EPSPS). Examples of such EPSPS genes are the AroA gene (mutant CT7) of the bacterium Salmonella typhimurium (Comai et al., 1983, Science 221, 370-371), the CP4 gene of the bacterium Agrobacterium sp. (Barry et al., 1992, Curr. Topics Plant Physiol. 7, 139-145), the genes encoding a Petunia EPSPS (Shah et al., 1986, Science 233, 478-481), a Tomato EPSPS (Gasser et al., 1988, J. Biol. Chem. 263, 4280-4289), or an Eleusine EPSPS (WO 01/66704). It can also be a mutated EPSPS as described in for example EP 0837944, WO 00/66746, WO 00/66747 or WO02/26995. Glyphosate-tolerant plants can also be obtained by expressing a gene that encodes a glyphosate oxido-reductase enzyme as described in U.S. Pat. Nos. 5,776,760 and 5,463,175. Glyphosate-tolerant plants can also be obtained by expressing a gene that encodes a glyphosate acetyl transferase enzyme as described in for example WO 02/36782, WO 03/092360, WO 05/012515 and WO 07/024,782. Glyphosate-tolerant plants can also be obtained by selecting plants containing naturally-occurring mutations of the above-mentioned genes, as described in for example WO 01/024615 or WO 03/013226. Plants expressing EPSPS genes that confer glyphosate tolerance are described in e.g. U.S. patent application Ser. Nos. 11/517,991, 10/739,610, 12/139,408, 12/352,532, 11/312,866, 11/315,678, 12/421,292, 11/400,598, 11/651,752, 11/681,285, 11/605,824, 12/468,205, 11/760,570, 11/762,526, 11/769,327, 11/769,255, 11/943,801 or 12/362,774. Plants comprising other genes that confer glyphosate tolerance, such as decarboxylase genes, are described in e.g. U.S. patent application Ser. Nos. 11/588,811, 11/185,342, 12/364,724, 11/185,560 or 12/423,926.

Other herbicide resistant plants are for example plants that are made tolerant to herbicides inhibiting the enzyme glutamine synthase, such as bialaphos, phosphinothricin or glufosinate. Such plants can be obtained by expressing an enzyme detoxifying the herbicide or a mutant glutamine synthase enzyme that is resistant to inhibition, e.g. described in U.S. patent application Ser. No. 11/760,602. One such efficient detoxifying enzyme is an enzyme encoding a phosphinothricin acetyltransferase (such as the bar or pat protein from Streptomyces species). Plants expressing an exogenous phosphinothricin acetyltransferase are for example described in U.S. Pat. Nos. 5,561,236; 5,648,477; 5,646,024; 5,273,894; 5,637,489; 5,276,268; 5,739,082; 5,908,810 and 7,112,665.

Further herbicide-tolerant plants are also plants that are made tolerant to the herbicides inhibiting the enzyme hydroxphenylpyruvatedioxygenase (HPPD). Hydroxphenylpyruvatedioxnenases are enzymes that catalyze the reaction in which para-hydroxyphenylpyruvate (HPP) is transformed into homogentisate. Plants tolerant to HPPD-inhibitors can be transformed with a gene encoding a naturally-occurring resistant HPPD enzyme, or a gene encoding a mutated or chimeric HPPD enzyme as described in WO 96/38567, WO 99/24585, WO 99/24586, WO 2009/144079, WO 2002/046387, or U.S. Pat. No. 6,768,044. Tolerance to HPPD-inhibitors can also be obtained by transforming plants with genes encoding certain enzymes enabling the formation of homogentisate despite the inhibition of the native HPPD enzyme by the HPPD-inhibitor. Such plants and genes are described in WO 99/34008 and WO 02/36787. Tolerance of plants to HPPD inhibitors can also be improved by transforming plants with a gene encoding an enzyme having prephenate deshydrogenase (PDH) activity in addition to a gene encoding an HPPD-tolerant enzyme, as described in WO 2004/024928. Further, plants can be made more tolerant to HPPD-inhibitor herbicides by adding into their genome a gene encoding an enzyme capable of metabolizing or degrading HPPD inhibitors, such as the CYP450 enzymes shown in WO 2007/103567 and WO 2008/150473.

Still further herbicide resistant plants are plants that are made tolerant to acetolactate synthase (ALS) inhibitors. Known ALS-inhibitors include, for example, sulfonylurea, imidazolinone, triazolopyrimidines, pryimidinyoxy(thio)benzoates, and/or sulfonylaminocarbonyltriazolinone herbicides. Different mutations in the ALS enzyme (also known as acetohydroxyacid synthase, AHAS) are known to confer tolerance to different herbicides and groups of herbicides, as described for example in Tranel and Wright (2002, Weed Science 50:700-712), but also, in U.S. Pat. Nos. 5,605,011, 5,378,824, 5,141,870, and 5,013,659. The production of sulfonylurea-tolerant plants and imidazolinone-tolerant plants is described in U.S. Pat. Nos. 5,605,011; 5,013,659; 5,141,870; 5,767,361; 5,731,180; 5,304,732; 4,761,373; 5,331,107; 5,928,937; and 5,378,824; and international publication WO 96/33270. Other imidazolinone-tolerant plants are also described in for example WO 2004/040012, WO 2004/106529, WO 2005/020673, WO 2005/093093, WO 2006/007373, WO 2006/015376, WO 2006/024351, and WO 2006/060634. Further sulfonylurea- and imidazolinone-tolerant plants are also described in for example WO 07/024,782 and U.S. Patent Application No. 61/288,958.

Other plants tolerant to imidazolinone and/or sulfonylurea can be obtained by induced mutagenesis, selection in cell cultures in the presence of the herbicide or mutation breeding as described for example for soybeans in U.S. Pat. No. 5,084,082, for rice in WO 97/41218, for sugar beet in U.S. Pat. No. 5,773,702 and WO 99/057965, for lettuce in U.S. Pat. No. 5,198,599, or for sunflower in WO 01/065922.

Plants or plant cultivars (obtained by plant biotechnology methods such as genetic engineering) which may also be treated according to the invention are insect-resistant transgenic plants, i.e. plants made resistant to attack by certain target insects. Such plants can be obtained by genetic transformation, or by selection of plants containing a mutation imparting such insect resistance.

An “insect-resistant transgenic plant”, as used herein, includes any plant containing at least one transgene comprising a coding sequence encoding:

-   -   1) an insecticidal crystal protein from Bacillus thuringiensis         or an insecticidal portion thereof, such as the insecticidal         crystal proteins listed by Crickmore et al. (1998, Microbiology         and Molecular Biology Reviews, 62: 807-813), updated by         Crickmore et al. (2005) at the Bacillus thuringiensis toxin         nomenclature, online at:         http://www.lifesci.sussex.ac.uk/Home/Neil_Crickmore/Bt/), or         insecticidal portions thereof, e.g., proteins of the Cry protein         classes Cry1Ab, Cry1Ac, Cry1B, Cry1C, Cry1D, Cry1F, Cry2Ab,         Cry3Aa, or Cry3Bb or insecticidal portions thereof (e.g. EP         1999141 and WO 2007/107302), or such proteins encoded by         synthetic genes as e.g. described in and U.S. patent application         Ser. No. 12/249,016; or     -   2) a crystal protein from Bacillus thuringiensis or a portion         thereof which is insecticidal in the presence of a second other         crystal protein from Bacillus thuringiensis or a portion         thereof, such as the binary toxin made up of the Cry34 and Cry35         crystal proteins (Moellenbeck et al. 2001, Nat. Biotechnol. 19:         668-72; Schnepf et al. 2006, Applied Environm. Microbiol. 71,         1765-1774) or the binary toxin made up of the Cry1A or Cry1F         proteins and the Cry2Aa or Cry2Ab or Cry2Ae proteins (U.S.         patent application Ser. No. 12/214,022 and EP 08010791.5); or     -   3) a hybrid insecticidal protein comprising parts of different         insecticidal crystal proteins from Bacillus thuringiensis, such         as a hybrid of the proteins of 1) above or a hybrid of the         proteins of 2) above, e.g., the Cry1A. 105 protein produced by         corn event MON89034 (WO 2007/027777); or 4) a protein of any one         of 1) to 3) above wherein some, particularly 1 to 10, amino         acids have been replaced by another amino acid to obtain a         higher insecticidal activity to a target insect species, and/or         to expand the range of target insect species affected, and/or         because of changes introduced into the encoding DNA during         cloning or transformation, such as the Cry3Bb1 protein in corn         events MON863 or MON88017, or the Cry3A protein in corn event         MIR604; or     -   5) an insecticidal secreted protein from Bacillus thuringiensis         or Bacillus cereus, or an insecticidal portion thereof, such as         the vegetative insecticidal (VIP) proteins listed at:         http://www.lifesci.sussex.ac.uk/home/Neil_Crickmore/Bt/vip.html,         e.g., proteins from the VIP3Aa protein class; or     -   6) a secreted protein from Bacillus thuringiensis or Bacillus         cereus which is insecticidal in the presence of a second         secreted protein from Bacillus thuringiensis or B. cereus, such         as the binary toxin made up of the VIP1A and VIP2A proteins (WO         94/21795); or     -   7) a hybrid insecticidal protein comprising parts from different         secreted proteins from Bacillus thuringiensis or Bacillus         cereus, such as a hybrid of the proteins in 1) above or a hybrid         of the proteins in 2) above; or     -   8) a protein of any one of 5) to 7) above wherein some,         particularly 1 to 10, amino acids have been replaced by another         amino acid to obtain a higher insecticidal activity to a target         insect species, and/or to expand the range of target insect         species affected, and/or because of changes introduced into the         encoding DNA during cloning or transformation (while still         encoding an insecticidal protein), such as the VIP3Aa protein in         cotton event COT102; or     -   9) a secreted protein from Bacillus thuringiensis or Bacillus         cereus which is insecticidal in the presence of a crystal         protein from Bacillus thuringiensis, such as the binary toxin         made up of VIP3 and Cry1A or Cry1F (U.S. Patent Appl. No.         61/126,083 and 61/195,019), or the binary toxin made up of the         VIP3 protein and the Cry2Aa or Cry2Ab or Cry2Ae proteins (U.S.         patent application Ser. No. 12/214,022 and EP 08010791.5).     -   10) a protein of 9) above wherein some, particularly 1 to 10,         amino acids have been replaced by another amino acid to obtain a         higher insecticidal activity to a target insect species, and/or         to expand the range of target insect species affected, and/or         because of changes introduced into the encoding DNA during         cloning or transformation (while still encoding an insecticidal         protein)

Of course, an insect-resistant transgenic plant, as used herein, also includes any plant comprising a combination of genes encoding the proteins of any one of the above classes 1 to 10. In one embodiment, an insect-resistant plant contains more than one transgene encoding a protein of any one of the above classes 1 to 10, to expand the range of target insect species affected when using different proteins directed at different target insect species, or to delay insect resistance development to the plants by using different proteins insecticidal to the same target insect species but having a different mode of action, such as binding to different receptor binding sites in the insect.

An “insect-resistant transgenic plant”, as used herein, further includes any plant containing at least one transgene comprising a sequence producing upon expression a double-stranded RNA which upon ingestion by a plant insect pest inhibits the growth of this insect pest, as described e.g. in WO 2007/080126, WO 2006/129204, WO 2007/074405, WO 2007/080127 and WO 2007/035650.

Plants or plant cultivars (obtained by plant biotechnology methods such as genetic engineering) which may also be treated according to the invention are tolerant to abiotic stresses. Such plants can be obtained by genetic transformation, or by selection of plants containing a mutation imparting such stress resistance. Particularly useful stress tolerance plants include:

-   -   1) plants which contain a transgene capable of reducing the         expression and/or the activity of poly(ADP-ribose) polymerase         (PARP) gene in the plant cells or plants as described in WO         00/04173, WO/2006/045633, EP 04077984.5, or EP 06009836.5.     -   2) plants which contain a stress tolerance enhancing transgene         capable of reducing the expression and/or the activity of the         PARG encoding genes of the plants or plants cells, as described         e.g. in WO 2004/090140.     -   3) plants which contain a stress tolerance enhancing transgene         coding for a plant-functional enzyme of the nicotineamide         adenine dinucleotide salvage synthesis pathway including         nicotinamidase, nicotinate phosphoribosyltransferase, nicotinic         acid mononucleotide adenyl transferase, nicotinamide adenine         dinucleotide synthetase or nicotine amide         phosphorybosyltransferase as described e.g. in EP 04077624.7, WO         2006/133827, PCT/EP07/002,433, EP 1999263, or WO 2007/107326.

Plants or plant cultivars (obtained by plant biotechnology methods such as genetic engineering) which may also be treated according to the invention show altered quantity, quality and/or storage-stability of the harvested product and/or altered properties of specific ingredients of the harvested product such as:

-   -   1) transgenic plants which synthesize a modified starch, which         in its physical-chemical characteristics, in particular the         amylose content or the amylose/amylopectin ratio, the degree of         branching, the average chain length, the side chain         distribution, the viscosity behaviour, the gelling strength, the         starch grain size and/or the starch grain morphology, is changed         in comparison with the synthesised starch in wild type plant         cells or plants, so that this is better suited for special         applications. Said transgenic plants synthesizing a modified         starch are disclosed, for example, in EP 0571427, WO 95/04826,         EP 0719338, WO 96/15248, WO 96/19581, WO 96/27674, WO 97/11188,         WO 97/26362, WO 97/32985, WO 97/42328, WO 97/44472, WO 97/45545,         WO 98/27212, WO 98/40503, WO99/58688, WO 99/58690, WO 99/58654,         WO 00/08184, WO 00/08185, WO 00/08175, WO 00/28052, WO 00/77229,         WO 01/12782, WO 01/12826, WO 02/101059, WO 03/071860, WO         2004/056999, WO 2005/030942, WO 2005/030941, WO 2005/095632, WO         2005/095617, WO 2005/095619, WO 2005/095618, WO 2005/123927, WO         2006/018319, WO 2006/103107, WO 2006/108702, WO 2007/009823, WO         00/22140, WO 2006/063862, WO 2006/072603, WO 02/034923, EP         06090134.5, EP 06090228.5, EP 06090227.7, EP 07090007.1, EP         07090009.7, WO 01/14569, WO 02/79410, WO 03/33540, WO         2004/078983, WO 01/19975, WO 95/26407, WO 96/34968, WO 98/20145,         WO 99/12950, WO 99/66050, WO 99/53072, U.S. Pat. No. 6,734,341,         WO 00/11192, WO 98/22604, WO 98/32326, WO 01/98509, WO 01/98509,         WO 2005/002359, U.S. Pat. No. 5,824,790, U.S. Pat. No.         6,013,861, WO 94/04693, WO 94/09144, WO 94/11520, WO 95/35026,         WO 97/20936     -   2) transgenic plants which synthesize non starch carbohydrate         polymers or which synthesize non starch carbohydrate polymers         with altered properties in comparison to wild type plants         without genetic modification. Examples are plants producing         polyfructose, especially of the inulin and levan-type, as         disclosed in EP 0663956, WO 96/01904, WO 96/21023, WO 98/39460,         and WO 99/24593, plants producing alpha-1,4-glucans as disclosed         in WO 95/31553, US 2002031826, U.S. Pat. No. 6,284,479, U.S.         Pat. No. 5,712,107, WO 97/47806, WO 97/47807, WO 97/47808 and WO         00/14249, plants producing alpha-1,6 branched alpha-1,4-glucans,         as disclosed in WO 00/73422, plants producing alternan, as         disclosed in e.g. WO 00/47727, WO 00/73422, EP 06077301.7, U.S.         Pat. No. 5,908,975 and EP 0728213,     -   3) transgenic plants which produce hyaluronan, as for example         disclosed in WO 2006/032538, WO 2007/039314, WO 2007/039315, WO         2007/039316, JP 2006304779, and WO 2005/012529.     -   4) transgenic plants or hybrid plants, such as onions with         characteristics such as ‘high soluble solids content’, ‘low         pungency’ (LP) and/or ‘long storage’ (LS), as described in U.S.         patent application Ser. No. 12/020,360 and 61/054,026.

Plants or plant cultivars (that can be obtained by plant biotechnology methods such as genetic engineering) which may also be treated according to the invention are plants, such as cotton plants, with altered fiber characteristics. Such plants can be obtained by genetic transformation, or by selection of plants contain a mutation imparting such altered fiber characteristics and include:

-   -   a) Plants, such as cotton plants, containing an altered form of         cellulose synthase genes as described in WO 98/00549     -   b) Plants, such as cotton plants, containing an altered form of         rsw2 or rsw3 homologous nucleic acids as described in WO         2004/053219     -   c) Plants, such as cotton plants, with increased expression of         sucrose phosphate synthase as described in WO 01/17333     -   d) Plants, such as cotton plants, with increased expression of         sucrose synthase as described in WO 02/45485     -   e) Plants, such as cotton plants, wherein the timing of the         plasmodesmatal gating at the basis of the fiber cell is altered,         e.g. through downregulation of fiber-selective β-1,3-glucanase         as described in WO 2005/017157, or as described in EP 08075514.3         or U.S. Patent Appl. No. 61/128,938     -   f) Plants, such as cotton plants, having fibers with altered         reactivity, e.g. through the expression of         N-acetylglucosaminetransferase gene including nodC and chitin         synthase genes as described in WO 2006/136351

Plants or plant cultivars (that can be obtained by plant biotechnology methods such as genetic engineering) which may also be treated according to the invention are plants, such as oilseed rape or related Brassica plants, with altered oil profile characteristics. Such plants can be obtained by genetic transformation, or by selection of plants contain a mutation imparting such altered oil profile characteristics and include:

-   -   a) Plants, such as oilseed rape plants, producing oil having a         high oleic acid content as described e.g. in U.S. Pat. No.         5,969,169, U.S. Pat. No. 5,840,946 or U.S. Pat. No. 6,323,392 or         U.S. Pat. No. 6,063,947     -   b) Plants such as oilseed rape plants, producing oil having a         low linolenic acid content as described in U.S. Pat. No.         6,270,828, U.S. Pat. No. 6,169,190, or U.S. Pat. No. 5,965,755     -   c) Plant such as oilseed rape plants, producing oil having a low         level of saturated fatty acids as described e.g. in U.S. Pat.         No. 5,434,283 or U.S. patent application Ser. No. 12/668,303

Plants or plant cultivars (that can be obtained by plant biotechnology methods such as genetic engineering) which may also be treated according to the invention are plants, such as oilseed rape or related Brassica plants, with altered seed shattering characteristics. Such plants can be obtained by genetic transformation, or by selection of plants contain a mutation imparting such altered seed shattering characteristics and include plants such as oilseed rape plants with delayed or reduced seed shattering as described in U.S. Patent Appl. No. 61/135,230 WO09/068,313 and WO10/006,732.

Particularly useful transgenic plants which may be treated according to the invention are plants containing transformation events, or combination of transformation events, that are the subject of petitions for nonregulated status, in the United States of America, to the Animal and Plant Health Inspection Service (APHIS) of the United States Department of Agriculture (USDA) whether such petitions are granted or are still pending. At any time this information is readily available from APHIS (4700 River Road Riverdale, Md. 20737, USA), for instance on its internet site (URL http://www.aphis.usda.gov/brs/not_reg.html). On the filing date of this application the petitions for nonregulated status that were pending with APHIS or granted by APHIS were those listed in table B which contains the following information:

-   -   Petition: the identification number of the petition. Technical         descriptions of the transformation events can be found in the         individual petition documents which are obtainable from APHIS,         for example on the APHIS website, by reference to this petition         number. These descriptions are herein incorporated by reference.     -   Extension of Petition: reference to a previous petition for         which an extension is requested.     -   Institution: the name of the entity submitting the petition.     -   Regulated article: the plant species concerned.     -   Transgenic phenotype: the trait conferred to the plants by the         transformation event.     -   Transformation event or line: the name of the event or events         (sometimes also designated as lines or lines) for which         nonregulated status is requested.     -   APHIS documents: various documents published by APHIS in         relation to the Petition and which can be requested with APHIS.

Additional particularly useful plants containing single transformation events or combinations of transformation events are listed for example in the databases from various national or regional regulatory agencies (see for example http://gmoinfo.jrc.it/gmp_browse.aspx and http://www.agbios.com/dbase.php).

Further particularly transgenic plants include plants containing a transgene in an agronomically neutral or beneficial position as described in any of the patent publications listed in Table C.

TABLE A Trait Reference Water use efficiency WO 2000/073475 Nitrogen use efficiency WO 1995/009911 WO 2007/076115 WO 1997/030163 WO 2005/103270 WO 2007/092704 WO 2002/002776 Improved photosynthesis WO 2008/056915 WO 2004/101751 Nematode resistance WO 1995/020669 WO 2003/033651 WO 2001/051627 WO 1999/060141 WO 2008/139334 WO 1998/012335 WO 2008/095972 WO 1996/030517 WO 2006/085966 WO 1993/018170 Reduced pod dehiscence WO 2006/009649 WO 1997/013865 WO 2004/113542 WO 1996/030529 WO 1999/015680 WO 1994/023043 WO 1999/000502 Aphid resistance WO 2006/125065 WO 2008/067043 WO 1997/046080 WO 2004/072109 Sclerotinia resistance WO 2006/135717 WO 2005/000007 WO 2006/055851 WO 2002/099385 WO 2005/090578 WO 2002/061043 Botrytis resistance WO 2006/046861 WO 2002/085105 Bremia resistance US 20070022496 WO 2004/049786 WO 2000/063432 Erwinia resistance WO 2004/049786 Closterovirus resistance WO 2007/073167 WO 2002/022836 WO 2007/053015 Stress tolerance (including WO 2010/019838 WO 2008/002480 drought tolerance) WO 2009/049110 WO 2005/033318 Tobamovirus resistance WO 2006/038794

TABLE B Petitions of Nonregulated Status Granted or Pending by APHIS as of Mar. 31, 2010 Applicant Documents Extension of Petition Regulated Transgenic Transformation Petition Number *** Institution Article Phenotype Event or Line Petitions for Nonregulated Status Pending 10-070-01p Virginia Tech Peanut Sclerotinia blight resistant N70, P39, and W171 09-349-01p Dow AgroSciences Soybean Herbicide Tolerant DAS-68416-4 09-328-01p Bayer Crop Science Soybean Herbicide Tolerant FG72 09-233-01p Dow Corn Herbicide Tolerant DAS-40278-9 09-201-01p Monsanto Soybean MON-877Ø5-6 09-183-01p Monsanto Soybean MON-87769 09-082-01p Monsanto Soybean Lepidopteran resistant MON 87701 09-063-01p Stine Seed Corn Glyphosate tolerant HCEM485 09-055-01p Monsanto Corn Drought Tolerant MON 87460 09-015-01p BASF Plant Soybean Herbicide Tolerant BPS-CV127-9 Science, LLC Soybean 08-366-01p ArborGen Eucalyptus Freeze Tolerant, ARB-FTE1-08 Fertility Altered 08-340-01p Bayer Cotton Glufosinate Tolerant, T304-40XGHB119 Insect Resistant 08-338-01p Pioneer Corn Male Sterile, Fertility DP-32138-1 Restored, Visual Marker 08-315-01p Florigene Rose Altered Flower Color IFD-524Ø1-4 and IFD-529Ø1-9 07-253-01p Syngenta Corn Lepidopteran resistant MIR-162 Maize 07-108-01p Syngenta Cotton Lepidopteran Resistant COT67B 06-354-01p Pioneer Soybean High Oleic Acid DP-3Ø5423-1 05-280-01p Syngenta Corn Thermostable alpha- 3272 amylase 04-110-01p Monsanto & Alfalfa Glyphosate Tolerant J101, J163 Forage Genetics 03-104-01p Monsanto & Creeping Glyphosate Tolerant ASR368 Scotts bentgrass Petitions for Nonregulated Status Granted 07-152-01p Pioneer Corn glyphosate & DP-098140-6 Imidazolinone tolerant 04-337-01p University of Papaya Papaya Ringspot Virus X17-2 Florida Resistant 06-332-01p Bayer CropScience Cotton Glyphosate tolerant GHB614 06-298-01p Monsanto Corn European Corn Borer MON 89034 resistant 06-271-01p Pioneer Soybean Glyphosate & acetolactate 356043 synthase tolerant (DP-356Ø43-5) 06-234-01p 98-329-01p Bayer CropScience Rice Phosphinothricin tolerant LLRICE601 06-178-01p Monsanto Soybean Glyphosate tolerant MON 89788 04-362-01p Syngenta Corn Corn Rootworm Protected MIR604 04-264-01p ARS Plum Plum Pox Virus Resistant C5 04-229-01p Monsanto Corn High Lysine LY038 04-125-01p Monsanto Corn Corn Rootworm Resistant 88017 04-086-01p Monsanto Cotton Glyphosate Tolerant MON 88913 03-353-01p Dow Corn Corn Rootworm Resistant 59122 03-323-01p Monsanto Sugar Beet Glyphosate Tolerant H7-1 03-181-01p 00-136-01p Dow Corn Lepidopteran Resistant & TC-6275 Phosphinothricin tolerant 03-155-01p Syngenta Cotton Lepidopteran Resistant COT 102 03-036-01p Mycogen/Dow Cotton Lepidopteran Resistant 281-24-236 03-036-02p Mycogen/Dow Cotton Lepidopteran Resistant 3006-210-23 02-042-01p Aventis Cotton Phosphinothericin tolerant LLCotton25 01-324-01p 98-216-01p Monsanto Rapeseed Glyphosate tolerant RT200 01-206-01p 98-278-01p Aventis Rapeseed Phosphinothricin tolerant & MS1 & RF1/RF2 pollination control 01-206-02p 97-205-01p Aventis Rapeseed Phosphinothricin tolerant Topas 19/2 01-137-01p Monsanto Corn Corn Rootworm Resistant MON 863 01-121-01p Vector Tobacco Reduced nicotine Vector 21-41 00-342-01p Monsanto Cotton Lepidopteran resistant Cotton Event 15985 00-136-01p Mycogen c/o Corn Lepidopteran resistant Line 1507 Dow & Pioneer phosphinothricin tolerant 00-011-01p 97-099-01p Monsanto Corn Glyphosate tolerant NK603 99-173-01p 97-204-01p Monsanto Potato PLRV & CPB resistant RBMT22-82 98-349-01p 95-228-01p AgrEvo Corn Phosphinothricin MS6 tolerant and Male sterile 98-335-01p U. of Flax Tolerant to soil CDC Triffid Saskatchewan residues of sulfonyl urea herbicide 98-329-01p AgrEvo Rice Phosphinothricin tolerant LLRICE06, LLRICE62 98-278-01p AgrEvo Rapeseed Phosphinothricin tolerant & MS8 & RF3 Pollination control 98-238-01p AgrEvo Soybean Phosphinothricin tolerant GU262 98-216-01p Monsanto Rapeseed Glyphosate tolerant RT73 98-173-01p Novartis Seeds & Beet Glyphosate tolerant GTSB77 Monsanto 98-014-01p 96-068-01p AgrEvo Soybean Phosphinothricin tolerant A5547-127 97-342-01p Pioneer Corn Male sterile & 676, 678, 680 Phosphinothricin tolerant 97-339-01p Monsanto Potato CPB & PVY resistant RBMT15-101, SEMT15-02, SEMT 15-15 97-336-01p AgrEvo Beet Phosphinothricin tolerant T-120-7 97-287-01p Monsanto Tomato Lepidopteran resistant 5345 97-265-01p AgrEvo Corn Phosphinothricin CBH-351 tolerant & Lep. resistant 97-205-01p AgrEvo Rapeseed Phosphinothricin tolerant T45 97-204-01p Monsanto Potato CPB & PLRV resistant RBMT21-129 & RBMT21-350 97-148-01p Bejo Cichorium Male sterile RM3-3, RM3-4, intybus RM3-6 97-099-01p Monsanto Corn Glyphosate tolerant GA21 97-013-01p Calgene Cotton Bromoxynil tolerant & Events 31807 & Lepidopteran resistant 31808 97-008-01p Du Pont Soybean Oil profile altered G94-1, G94-19, G-168 96-317-01p Monsanto Corn Glyphosate tolerant & MON802 ECB resistant 96-291-01p DeKalb Corn European Corn Borer DBT418 resistant 96-248-01p 92-196-01p Calgene Tomato Fruit ripening altered 1 additional FLAVRSAVR line 96-068-01p AgrEvo Soybean Phosphinothricin W62, W98, A2704- tolerant 12, A2704-21, A5547-35 96-051-01p Cornell U Papaya PRSV resistant 55-1, 63-1 96-017-01p 95-093-01p Monsanto Corn European Corn Borer MON809 & MON810 resistant 95-352-01p Asgrow Squash CMV, ZYMV, WMV2 CZW-3 resistant 95-338-01p Monsanto Potato CPB resistant SBT02-5 & -7, ATBT04-6 & -27, -30, -31, -36 95-324-01p Agritope Tomato Fruit ripening altered 35 1 N 95-256-01p Du Pont Cotton Sulfonylurea tolerant 19-51a 95-228-01p Plant Genetic Corn Male sterile MS3 Systems 95-195-01p Northrup King Corn European Corn Borer Bt11 resistant 95-179-01p 92-196-01p Calgene Tomato Fruit ripening altered 2 additional FLAVRSAVR lines 95-145-01p DeKalb Corn Phosphinothricin tolerant B16 95-093-01p Monsanto Corn Lepidopteran resistant MON 80100 95-053-01p Monsanto Tomato Fruit ripening altered 8338 95-045-01p Monsanto Cotton Glyphosate tolerant 1445, 1698 95-030-01p 92-196-01p Calgene Tomato Fruit ripening altered 20 additional FLAVRSAVR lines 94-357-01p AgrEvo Corn Phosphinothricin tolerant T14, T25 94-319-01p Ciba Seeds Corn Lepidopteran resistant Event 176 94-308-01p Monsanto Cotton Lepidopteran resistant 531, 757, 1076 94-290-01p Zeneca & Tomato Fruit polygalacturonase B, Da, F Petoseed level decreased 94-257-01p Monsanto Potato Coleopteran resistant BT6, BT10, BT12, BT16, BT17, BT18, BT23 94-230-01p 92-196-01p Calgene Tomato Fruit ripening altered 9 additional FLAVRSAVR lines 94-228-01p DNA Plant Tech Tomato Fruit ripening altered 1345-4 94-227-01p 92-196-01p Calgene Tomato Fruit ripening altered Line N73 1436-111 94-090-01p Calgene Rapeseed Oil profile altered pCGN3828-212/86-18 & 23 93-258-01p Monsanto Soybean Glyphosate tolerant 40-3-2 93-196-01p Calgene Cotton Bromoxynil tolerant BXN 92-204-01p Upjohn Squash WMV2 & ZYMV ZW-20 resistant 92-196-01p Calgene Tomato Fruit ripening altered FLAVR SAVR NOTE: To obtain the most up-to-date list of Crops No Longer Regulated, please look at the Current Status of Petitions. This list is automatically updated and reflects all petitions received to date by APHIS, including petitions pending, withdrawn, or approved. Abbreviations: CMV—cucumber mosaic virus; CPB—colorado potato beetle; PLRV—potato leafroll virus; PRSV—papaya ringspot virus; PVY—potato virus Y; WMV2—watermelon mosaic virus 2 ZYMV—zucchini yellow mosaic virus *** Extension of Petition Number: Under 7CFR 340.6(e) a person may request that APHIS extend a determination of non-regulated status to other organisms based on their similarity of the previously deregulated article. This column lists the previously granted petition of that degregulated article. **** Preliminary EA: The Environmental Assessment initially available for Public comment prior to finalization.

TABLE C Plant species Event Trait Patent reference Corn PV-ZMGT32 (NK603) Glyphosate tolerance US 2007-056056 Corn MIR604 Insect resistance (Cry3a055) EP 1 737 290 Corn LY038 High lysine content U.S. Pat. No. 7,157,281 Corn 3272 Self processing corn (alpha- US 2006-230473 amylase) Corn PV-ZMIR13 Insect resistance (Cry3Bb) US 2006-095986 (MON863) Corn DAS-59122-7 Insect resistance US 2006-070139 (Cry34Ab1/Cry35Ab1) Corn TC1507 Insect resistance (Cry1F) U.S. Pat. No. 7,435,807 Corn MON810 Insect resistance (Cry1Ab) US 2004-180373 Corn VIP1034 Insect resistance WO 03/052073 Corn B16 Glufosinate resistance US 2003-126634 Corn GA21 Glyphosate resistance U.S. Pat. No. 6,040,497 Corn GG25 Glyphosate resistance U.S. Pat. No. 6,040,497 Corn GJ11 Glyphosate resistance U.S. Pat. No. 6,040,497 Corn FI117 Glyphosate resistance U.S. Pat. No. 6,040,497 Corn GAT-ZM1 Glufosinate tolerance WO 01/51654 Corn MON87460 Drought tolerance WO 2009/111263 Corn DP-098140-6 Glyphosate tolerance/ALS WO 2008/112019 inhibitor tolerance Wheat Event 1 Fusarium resistance CA 2561992 (trichothecene 3-O- acetyltransferase) Sugar beet T227-1 Glyphosate tolerance US 2004-117870 Sugar beet H7-1 Glyphosate tolerance WO 2004-074492 Soybean MON89788 Glyphosate tolerance US 2006-282915 Soybean A2704-12 Glufosinate tolerance WO 2006/108674 Soybean A5547-35 Glufosinate tolerance WO 2006/108675 Soybean DP-305423-1 High oleic acid/ALS inhibitor WO 2008/054747 tolerance Rice GAT-OS2 Glufosinate tolerance WO 01/83818 Rice GAT-OS3 Glufosinate tolerance US 2008-289060 Rice PE-7 Insect resistance (Cry1Ac) WO 2008/114282 Oilseed rape MS-B2 Male sterility WO 01/31042 Oilseed rape MS-BN1/RF-BN1 Male sterility/restoration WO 01/41558 Oilseed rape RT73 Glyphosate resistance WO 02/36831 Cotton CE43-67B Insect resistance (Cry1Ab) WO 2006/128573 Cotton CE46-02A Insect resistance (Cry1Ab) WO 2006/128572 Cotton CE44-69D Insect resistance (Cry1Ab) WO 2006/128571 Cotton 1143-14A Insect resistance (Cry1Ab) WO 2006/128569 Cotton 1143-51B Insect resistance (Cry1Ab) WO 2006/128570 Cotton T342-142 Insect resistance (Cry1Ab) WO 2006/128568 Cotton event3006-210-23 Insect resistance (Cry1Ac) WO 2005/103266 Cotton PV-GHGT07 (1445) Glyphosate tolerance US 2004-148666 Cotton MON88913 Glyphosate tolerance WO 2004/072235 Cotton EE-GH3 Glyphosate tolerance WO 2007/017186 Cotton T304-40 Insect-resistance (Cry1Ab) WO2008/122406 Cotton Cot202 Insect resistance (VIP3) US 2007-067868 Cotton LLcotton25 Glufosinate resistance WO 2007/017186 Cotton EE-GH5 Insect resistance (Cry1Ab) WO 2008/122406 Cotton event 281-24-236 Insect resistance (Cry1F) WO 2005/103266 Cotton Cot102 Insect resistance (Vip3A) US 2006-130175 Cotton MON 15985 Insect resistance (Cry1A/Cry2Ab) US 2004-250317 Bent Grass Asr-368 Glyphosate tolerance US 2006-162007 Brinjal EE-1 Insect resistance (Cry1Ac) WO 2007/091277

Among the diseases of plants or crops that can be controlled by the method according to the invention, mention can be made of:

-   -   Powdery mildew diseases such as:         -   Blumeria diseases, caused for example by Blumeria graminis;         -   Podosphaera diseases, caused for example by Podosphaera             leucotricha;         -   Sphaerotheca diseases, caused for example by Sphaerotheca             fuliginea;         -   Uncinula diseases, caused for example by Uncinula necator;     -   Rust diseases such as:         -   Gymnosporangium diseases, caused for example by             Gymnosporangium sabinae;         -   Hemileia diseases, caused for example by Hemileia vastatrix;         -   Phakopsora diseases, caused for example by Phakopsora             pachyrhizi or Phakopsora meibomiae;         -   Puccinia diseases, caused for example by Puccinia recondite,             Puccinia graminis or Puccinia striiformis;         -   Uromyces diseases, caused for example by Uromyces             appendiculatus;     -   Oomycete diseases such as:         -   Albugo diseases caused for example by Albugo candida;         -   Bremia diseases, caused for example by Bremia lactucae;         -   Peronospora diseases, caused for example by Peronospora pisi             or P. brassicae;         -   Phytophthora diseases, caused for example by Phytophthora             infestans;         -   Plasmopara diseases, caused for example by Plasmopara             viticola;         -   Pseudoperonospora diseases, caused for example by             Pseudoperonospora humuli or Pseudoperonospora cubensis;         -   Pythium diseases, caused for example by Pythium ultimum;     -   Leafspot, leaf blotch and leaf blight diseases such as:         -   Alternaria diseases, caused for example by Alternaria             solani;         -   Cercospora diseases, caused for example by Cercospora             beticola;         -   Cladiosporum diseases, caused for example by Cladiosporium             cucumerinum;         -   Cochliobolus diseases, caused for example by Cochliobolus             sativus (Conidiaform: Drechslera, Syn: Helminthosporium) or             Cochliobolus miyabeanus;         -   Colletotrichum diseases, caused for example by             Colletotrichum lindemuthanium;         -   Cycloconium diseases, caused for example by Cycloconium             oleaginum;         -   Diaporthe diseases, caused for example by Diaporthe citri;         -   Elsinoe diseases, caused for example by Elsinoe fawcettii;         -   Gloeosporium diseases, caused for example by Gloeosporium             laeticolor;         -   Glomerella diseases, caused for example by Glomerella             cingulata;         -   Guignardia diseases, caused for example by Guignardia             bidwefli;         -   Leptosphaeria diseases, caused for example by Leptosphaeria             maculans; Leptosphaeria nodorum;         -   Magnaporthe diseases, caused for example by Magnaporthe             grisea;         -   Mycosphaerella diseases, caused for example by             Mycosphaerella graminicola; Mycosphaerella arachidicola;             Mycosphaerella fijiensis;         -   Phaeosphaeria diseases, caused for example by Phaeosphaeria             nodorum;         -   Pyrenophora diseases, caused for example by Pyrenophora             teres, or Pyrenophora tritici repentis;         -   Ramularia diseases, caused for example by Ramularia             collo-cygni, or Ramularia areola;         -   Rhynchosporium diseases, caused for example by             Rhynchosporium secalis;         -   Septoria diseases, caused for example by Septoria apii or             Septoria lycopercisi;         -   Typhula diseases, caused for example by Typhula incamata;         -   Venturia diseases, caused for example by Venturia             inaequalis;     -   Root, Sheath and stem diseases such as:         -   Corticium diseases, caused for example by Corticium             graminearum;         -   Fusarium diseases, caused for example by Fusarium oxysporum;         -   Gaeumannomyces diseases, caused for example by             Gaeumannomyces graminis;         -   Rhizoctonia diseases, caused for example by Rhizoctonia             solani;         -   Sarocladium diseases caused for example by Sarocladium             oryzae;         -   Sclerotium diseases caused for example by Sclerotium oryzae;         -   Tapesia diseases, caused for example by Tapesia acuformis;         -   Thielaviopsis diseases, caused for example by Thielaviopsis             basicola;     -   Ear and panicle diseases such as:         -   Alternaria diseases, caused for example by Alternaria spp.;         -   Aspergillus diseases, caused for example by Aspergillus             flavus;         -   Cladosporium diseases, caused for example by Cladosporium             spp.;         -   Claviceps diseases, caused for example by Claviceps             purpurea;         -   Fusarium diseases, caused for example by Fusarium culmorum;         -   Gibberella diseases, caused for example by Gibberella zeae;         -   Monographella diseases, caused for example by Monographella             nivalis;     -   Smut and bunt diseases such as:         -   Sphacelotheca diseases, caused for example by Sphacelotheca             reiliana;         -   Tilletia diseases, caused for example by Tilletia caries;         -   Urocystis diseases, caused for example by Urocystis occulta;         -   Ustilago diseases, caused for example by Ustilago nuda;     -   Fruit rot and mould diseases such as:         -   Aspergillus diseases, caused for example by Aspergillus             flavus;         -   Botrytis diseases, caused for example by Botrytis cinerea;         -   Penicillium diseases, caused for example by Penicillium             expansum;         -   Rhizopus diseases caused by example by Rhizopus stolonifer         -   Sclerotinia diseases, caused for example by Sclerotinia             sclerotiorum;         -   Verticilium diseases, caused for example by Verticilium             alboatrum;     -   Seed and soilbome decay, mould, wilt, rot and damping-off         diseases:         -   Alternaria diseases, caused for example by Alternaria             brassicicola         -   Aphanomyces diseases, caused for example by Aphanomyces             euteiches         -   Ascochyta diseases, caused for example by Ascochyta lentis         -   Aspergillus diseases, caused for example by Aspergillus             flavus         -   Cladosporium diseases, caused for example by Cladosporium             herbarum         -   Cochliobolus diseases, caused for example by Cochliobolus             sativus (Conidiaform: Drechslera, Bipolaris Syn:             Helminthosporium);         -   Colletotrichum diseases, caused for example by             Colletotrichum coccodes;         -   Fusarium diseases, caused for example by Fusarium culmorum;         -   Gibberella diseases, caused for example by Gibberella zeae;         -   Macrophomina diseases, caused for example by Macrophomina             phaseolina         -   Monographella diseases, caused for example by Monographella             nivalis;         -   Penicillium diseases, caused for example by Penicillium             expansum         -   Phoma diseases, caused for example by Phoma lingam         -   Phomopsis diseases, caused for example by Phomopsis sojae;         -   Phytophthora diseases, caused for example by Phytophthora             cactorum;         -   Pyrenophora diseases, caused for example by Pyrenophora             graminea         -   Pyricularia diseases, caused for example by Pyricularia             oryzae;         -   Pythium diseases, caused for example by Pythium ultimum;         -   Rhizoctonia diseases, caused for example by Rhizoctonia             solani;         -   Rhizopus diseases, caused for example by Rhizopus oryzae         -   Sclerotium diseases, caused for example by Sclerotium             rolfsii;         -   Septoria diseases, caused for example by Septoria nodorum;         -   Typhula diseases, caused for example by Typhula incarnata;         -   Verticillium diseases, caused for example by Verticillium             dahliae;     -   Canker, broom and dieback diseases such as:         -   Nectria diseases, caused for example by Nectria galligena;     -   Blight diseases such as:         -   Monilinia diseases, caused for example by Monilinia laxa;     -   Leaf blister or leaf curl diseases such as:         -   Exobasidium diseases caused for example by Exobasidium             vexans         -   Taphrina diseases, caused for example by Taphrina deformans;     -   Decline diseases of wooden plants such as:         -   Esca diseases, caused for example by Phaemoniella             clamydospora;         -   Eutypa dyeback, caused for example by Eutypa lata;         -   Ganoderma diseases caused for example by Ganoderma             boninense;         -   Rigidoporus diseases caused for example by Rigidoporus             lignosus     -   Diseases of Flowers and Seeds such as         -   Botrytis diseases caused for example by Botrytis cinerea;     -   Diseases of Tubers such as         -   Rhizoctonia diseases caused for example by Rhizoctonia             solani;         -   Helminthosporium diseases caused for example by             Helminthosporium solani;     -   Club root diseases such as         -   Plasmodiophora diseases, cause for example by Plamodiophora             brassicae.     -   Diseases caused by Bacterial Organisms such as         -   Xanthomonas species for example Xanthomonas campestris pv.             oryzae;         -   Pseudomonas species for example Pseudomonas syringae pv.             lachrymans;         -   Erwinia species for example Erwinia amylovora.

The composition according to the invention may also be used against fungal diseases liable to grow on or inside timber. The term “timber” means all types of species of wood, and all types of working of this wood intended for construction, for example solid wood, high-density wood, laminated wood, and plywood. The method for treating timber according to the invention mainly consists in contacting one or more compounds according to the invention or a composition according to the invention; this includes for example direct application, spraying, dipping, injection or any other suitable means.

The dose of active compound usually applied in the method of treatment according to the invention is generally and advantageously from 10 to 800 g/ha, preferably from 50 to 300 g/ha for applications in foliar treatment. The dose of active substance applied is generally and advantageously from 2 to 200 g per 100 kg of seed, preferably from 3 to 150 g per 100 kg of seed in the case of seed treatment.

It is clearly understood that the doses indicated herein are given as illustrative examples of the method according to the invention. A person skilled in the art will know how to adapt the application doses, notably according to the nature of the plant or crop to be treated.

The compounds or mixtures according to the invention can also be used for the preparation of composition useful to curatively or preventively treat human or animal fungal diseases such as, for example, mycoses, dermatoses, trichophyton diseases and candidiases or diseases caused by Aspergillus spp., for example Aspergillus fumigatus.

The various aspects of the invention will now be illustrated with reference to the following table of compound examples and the following preparation or efficacy examples.

Table 1 illustrates in a non-limiting manner examples of compounds of formula (I) wherein Z³ is hydrogen, according to the invention:

In table 1, unless otherwise specified, M+H (Apcl+) means the molecular ion peak plus 1 a.m.u. (atomic mass unit) as observed in mass spectroscopy via positive atmospheric pressure chemical ionisation.

In table 1, the log P values were determined in accordance with EEC Directive 79/831 Annex V.A8 by HPLC (High Performance Liquid Chromatography) on a reversed-phase column (C 18), using the method described below:

Temperature: 40° C.; Mobile phases: 0.1% aqueous formic acid and acetonitrile; linear gradient from 10% acetonitrile to 90% acetonitrile.

Calibration was carried out using unbranched alkan-2-ones (comprising 3 to 16 carbon atoms) with known log P values (determination of the log P values by the retention times using linear interpolation between two successive alkanones). lambda-max-values were determined using UV-spectra from 200 nm to 400 nm and the peak values of the chromatographic signals.

TABLE 1   Example   A   T   Z³   n

  Q¹   B   logP Mass (M + H) 1

O H 0 — — 2-methylphenyl 2.71 316 2

O H 0 — — 2-methylphenyl 3.19 313 3

O H 0 — — 2-methylphenyl 3.73 298 4

O H 0 — — 2-methylphenyl 3.06 330 5

O H 0 — — 2-methylphenyl 3.37 368 6

O H 0 — — 2-methylphenyl 3.21 352 7

S H 0 — — 2-methylphenyl 3.81 368 8

O H 0 — — 3,4-dimethylphenyl 3.87 382 9

O H 0 — — 3,4-dimethylphenyl 3.64 366 10

O H 0 — — 3,5-dimethylphenyl 3.23 330 11

O H 0 — — 3,5-dimethylphenyl 3.62 344 12

O H 0 — — 3,5-dimethylphenyl 4.34 312 13

O H 0 — — 3,5-dimethylphenyl 3.55 424 14

O H 0 — — 3,5-dimethylphenyl 3.09 343 15

O H 0 — — 3,5-dimethylphenyl 3.60 316 16

O H 0 — — 3,5-dimethylphenyl 4.59 344 17

O H 0 — — 3,5-dimethylphenyl 3.71 316 18

O H 0 — — 3,5-dimethylphenyl 3.55 376 19

O H 0 — — 3,5-dimethylphenyl 3.44 332 20

O H 0 — — 3,5-dimethylphenyl 3.67 344 21

O H 0 — — 3,5-dimethylphenyl 3.73 335 22

O H 0 — — 3,5-dimethylphenyl 4.59 399 23

O H 0 — — 3,5-dimethylphenyl 4.86 369 24

O H 0 — — 3,5-dimethylphenyl 3.85 380 25

O H 0 — — 3,5-dimethylphenyl 4.49 349 26

O H 0 — — 3,5-dimethylphenyl 4.51 393 27

O H 0 — — 3,5-dimethylphenyl 3.44 329 28

O H 0 — — 3,5-dimethylphenyl 4.06 349 29

O H 0 — — 3,5-dimethylphenyl 3.25 315 30

O H 0 — — 3,5-dimethylphenyl 3.71 366 31

O H 0 — — 3,5-dimethylphenyl 3.87 332 32

O H 0 — — 3,5-dimethylphenyl 4.34 346 33

O H 0 — — 3,5-dimethylphenyl 4.93 390 34

O H 0 — — 3,5-dimethylphenyl 4.27 383 35

O H 0 — — 3,5-dimethylphenyl 4.21 426 36

O H 0 — — 2-chlorophenyl 2.89 336 37

O H 0 — — 2-chlorophenyl 3.19 350 38

O H 0 — — 2-chlorophenyl 3.29 333 39

O H 0 — — 2-chlorophenyl 3.89 318 40

O H 0 — — 2-chlorophenyl 3.48 388 41

O H 0 — — 2-chlorophenyl 3.31 372 42

S H 0 — — 2-chlorophenyl 4.00 388 43

O H 0 — — 3-chlorophenyl 3.31 350 44

O H 0 — — 3-chlorophenyl 2.94 336 45

O H 0 — — 3-chlorophenyl 3.48 333 46

O H 0 — — 3-chlorophenyl 4.04 318 47

O H 0 — — 3-chlorophenyl 3.60 388 48

O H 0 — — 3-chlorophenyl 3.39 372 49

S H 0 — — 3-chlorophenyl 4.06 388 50

S H 0 — — 3-chlorophenyl 4.31 404 51

O H 0 — — 4-chlorophenyl 2.98 336 52

O H 0 — — 4-chlorophenyl 3.51 333 53

O H 0 — — 4-chlorophenyl 4.04 318 54

O H 0 — — 4-chlorophenyl 3.35 350 55

O H 0 — — 4-chlorophenyl 3.67 388 56

O H 0 — — 4-chlorophenyl 3.46 372 57

S H 0 — — 4-chlorophenyl 4.16 388 58

O H 0 — — 1,3-benzodioxol-5-yl 3.33 328 59

O H 0 — — 1,3-benzodioxol-5-yl 2.73 360 60

O H 0 — — 1,3-benzodioxol-5-yl 2.44 346 61

O H 0 — — 2,3-dihydro-1,4- benzodioxin-6-yl 2.82 357 62

O H 0 — — 2,3-dihydro-1,4- benzodioxin-6-yl 3.25 342 63

O H 0 — — 2,3-dihydro-1,4- benzodioxin-6-yl 2.66 374 64

O H 0 — — 2,3-dihydro-1,4- benzodioxin-6-yl 2.39 360 65

O H 0 — — 2,3-dihydro-1,4- benzodioxin-6-yl 2.75 396 66

O H 0 — — 2,3-dihydro-1,4- benzodioxin-6-yl 2.99 412 67

O H 0 — — 3,5-dimethoxyphenyl 2.84 376 68

O H 0 — — 3,5-dimethoxyphenyl 2.56 362 69

O H 0 — — 3,5-dimethoxyphenyl 3.02 359 70

O H 0 — — 3,5-dimethoxyphenyl 3.48 344 71

O H 0 — — 2,3-dichlorophenyl 4.29 352 72

O H 0 — — 2,3-dichlorophenyl 3.62 384 73

O H 0 — — 2,3-dichlorophenyl 3.25 370 74

O H 0 — — 2,3-dichlorophenyl 3.73 367 75

O H 0 — — 2,4-dichlorophenyl 3.60 386 76

O H 0 — — 2,4-dichlorophenyl 3.39 370 77

O H 0 — — 2,4-dichlorophenyl 3.89 367 78

O H 0 — — 2,4-dichlorophenyl 3.83 384 79

O H 0 — — 2,4-dichlorophenyl 4.54 352 80

O H 0 — — 2,4-dichlorophenyl 4.06 422 81

O H 0 — — 2,4-dichlorophenyl 3.87 406 82

O H 0 — — 2,5-dichlorophenyl 3.67 384 83

O H 0 — — 2,5-dichlorophenyl 3.29 370 84

O H 0 — — 2,5-dichlorophenyl 4.36 352 85

O H 0 — — 2,5-dichlorophenyl 3.78 367 86

O H 0 — — 2-bromophenyl 3.96 362 87

O H 0 — — 2-bromophenyl 3.25 394 88

O H 0 — — 2-bromophenyl 2.99 380 89

O H 0 — — 2-bromophenyl 3.35 377 90

O H 0 — — 2-bromophenyl 3.55 432 91

O H 0 — — 2-bromophenyl 3.39 416 92

S H 0 — — 2-bromophenyl 3.92 432 93

O H 0 — — 3-bromophenyl 4.11 362 94

O H 0 — — 3-bromophenyl 3.44 394 95

O H 0 — — 3-bromophenyl 3.06 380 96

O H 0 — — 3-bromophenyl 3.71 432 97

O H 0 — — 3-bromophenyl 3.51 416 98

S H 0 — — 3-bromophenyl 4.16 432 99

O H 0 — — 4-bromophenyl 3.11 380 100

O H 0 — — 4-bromophenyl 4.16 362 101

O H 0 — — 4-bromophenyl 3.64 377 102

O H 0 — — 4-bromophenyl 3.51 394 103

O H 0 — — 4-bromophenyl 3.78 432 104

O H 0 — — 4-bromophenyl 3.60 416 105

S H 0 — — 4-bromophenyl 4.29 432 106

O H 0 — — 3,4,5-trimethoxyphenyl 2.21 392 107

O H 0 — — 3,4,5-trimethoxyphenyl 2.64 389 108

O H 0 — — 3,4,5-trimethoxyphenyl 3.04 374 109

O H 0 — — 3,4,5-trimethoxyphenyl 2.49 406 110

O H 0 — — 3-phenoxyphenyl 4.16 391 111

O H 0 — — 3-phenoxyphenyl 4.65 376 112

O H 0 — — 3-phenoxyphenyl 3.96 408 113

O H 0 — — 3-phenoxyphenyl 3.60 394 114

O H 0 — — 3-phenoxyphenyl 4.18 446 115

O H 0 — — 3-phenoxyphenyl 3.99 430 116

O H 0 — — 3-iodophenyl 4.36 410 117

O H 0 — — 2-naphthyl 3.58 366 118

O H 0 — — 2-naphthyl 3.21 352 119

O H 0 — — 2-naphthyl 3.76 349 120

O H 0 — — 2-naphthyl 4.39 334 121

O H 0 — — 2-naphthyl 3.87 404 122

O H 0 — — 2-naphthyl 3.69 388 123

S H 0 — — 2-naphthyl 4.36 404 124

O H 0 — — 5-bromo-2-thienyl 3.13 386 125

O H 0 — — 5-bromo-2-thienyl 3.51 400 126

O H 0 — — 5-bromo-2-thienyl 3.67 383 127

O H 0 — — 5-bromo-2-thienyl 4.29 368 128

O H 0 — — 5-bromo-2-thienyl 3.55 400 129

O H 1 —CH₂— — phenyl 2.54 316 130

O H 1 —CH₂— — phenyl 3.11 313 131

O H 1 —CH₂— — phenyl 2.92 330 132

O H 1 —CH₂— — phenyl 3.58 298 133

O H 1 —CH₂— — phenyl 3.17 351 134

O H 1 —CH₂— — phenyl 3.09 352 135

O H 1 —CH(Et)— — phenyl 3.87 396 136

O H 1 —CH(Et)— — phenyl 3.59 380 137

O H 1 —CH(Me)— — phenyl 3.59 382 138

O H 1 —CH(Me)— — phenyl 3.39 366 139

S H 1 —CH(Me)— — phenyl 4.14 382 140

S H 1 —CH(Et)— — phenyl 4.39 396 141

O H 1 —CH₂— — 2-methylphenyl 3.87 312 142

O H 1 —CH₂— — 2-methylphenyl 3.50 365 143

O H 1 —CH₂— — 3-methylphenyl 3.96 312 144

O H 1 —CH₂— — 3-methylphenyl 3.44 366 145

O H 1 —CH₂— — 3-methylphenyl 3.57 365 146

O H 1 —CH₂— — 4-methylphenyl 3.99 312 147

O H 1 —CH₂— — 4-methylphenyl 3.46 366 148

O H 1 —CH₂— — 4-methylphenyl 3.59 365 149

O H 1 —CH₂— O 4-methylphenyl 3.55 398 150

O H 1 —CH₂— O 4-methylphenyl 3.35 382 151

O H 1 —CH₂— — 3-fluorophenyl 3.19 369 152

O H 1 —CH₂— — 3-fluorophenyl 3.59 316 153

O H 1 —CH₂— — 3-fluorophenyl 3.13 370 154

O H 1 —CH₂— — 4-fluorophenyl 3.21 369 155

O H 1 —CH₂— — 4-fluorophenyl 3.57 316 156

O H 1 —CH₂— — 4-fluorophenyl 3.11 370 157

O H 1 —CH₂— — 2-methoxyphenyl 3.17 382 158

O H 1 —CH₂— — 2-methoxyphenyl 3.63 328 159

O H 1 —CH₂— — 2-methoxyphenyl 3.33 381 160

S H 1 —CH₂— — 2-methoxyphenyl 3.87 398 161

O H 1 —CH(Et)— — 2-chlorophenyl 4.44 430 162

O H 1 —CH(Et)— — 2-chlorophenyl 4.13 414 163

O H 1 —CH(Me)— — 2-chlorophenyl 3.72 400 164

O H 1 —CH(Me)— — 2-chlorophenyl 4.06 416 165

S H 1 —CH(Et)— — 2-chlorophenyl 4.95 430 166

S H 1 —CH(Me)— — 2-chlorophenyl 4.53 416 167

O H 1 —CH₂— — 3-(trifluoromethyl) phenyl 3.70 419 168

O H 1 —CH₂— — 3-(trifluoromethyl) phenyl 4.06 366 169

O H 1 —CH₂— — 3-(trifluoromethyl) phenyl 3.59 420 170

O H 1 —CH₂— — 1-naphthyl 3.76 401 171

O H 1 —CH₂— — 1-naphthyl 3.65 402 172

O H 1 —CH₂— O 2-naphthyl 3.87 434 173

O H 1 —CH₂— O 2-naphthyl 3.68 418 174

O H 2 —CH₂CH₂— — phenyl 3.44 327 175

O H 2 —CH₂CH₂— — phenyl 3.92 312 176

O H 2 —CH₂CH₂— — phenyl 3.25 344 177

O H 2 —CH₂CH₂— — phenyl 3.37 366 178

O H 2 —CH₂CH₂— — phenyl 3.52 365 179

S H 2 —CH₂CH₂— — phenyl 4.06 382 180

O H 2 —CH₂CH₂— O 3,5-dimethylphenyl 4.11 426 181

O H 2 —CH₂CH₂— O 3,5-dimethylphenyl 3.92 410 182

O H 2 —CH₂CH₂— O 2,4-difluorophenyl 3.29 418 183

O H 2 —CH₂CH₂— O 2,4-difluorophenyl 3.46 434 184

O H 2 —CH₂CH₂— O 2,4-dichlorophenyl 4.26 466 185

O H 2 —CH₂CH₂— O 2,4-dichlorophenyl 4.06 450 186

O H 2 —CH₂CH₂— O biphenyl-2-yl 4.39 474 187

O H 2 —CH₂CH₂— O biphenyl-2-yl 4.21 458 188

O H 2 —CH₂CH₂— O biphenyl-4-yl 4.49 474 189

O H 2 —CH₂CH₂— O biphenyl-4-yl 4.31 458 190

O H 2 —CH₂CH₂— O 2-naphthyl 4.09 448 191

O H 2 —CH₂CH₂— O 2-naphthyl 3.92 432 192

O H 2 —CH₂CH₂— — 2-thienyl 3.35 371 193

O H 2 —CH₂CH₂— — 2-thienyl 3.79 318 194

O H 2 —CH₂CH₂— — 2-thienyl 3.25 372 195

O H 2 —CH₂CH₂— O 5-(trifluoromethyl) pyridin-2-yl 3.74 467 196

O H 2 —CH₂CH₂— O 5-(trifluoromethyl) pyridin-2-yl 3.57 451

Table 2 illustrates in a non-limiting manner examples of compounds of formula (I) wherein Z³ is methyl, according to the invention:

In table 2, M+H (Apcl+) and log P are defined as in table 1.

TABLE 2 Mass Example formula (I) logP (M + H) 197

3.55 366 198

3.73 382 199

3.17 348

The following examples illustrate in a non-limiting manner the preparation and efficacy of the compounds of formula (I) according to the invention.

PREPARATION EXAMPLE 1 Preparation of (5-fluoro-1,3-dimethyl-1H-pyrazol-4-yl)[2-(2-methylphenyl)-piperidin-1-yl]methanone (Compound 1)

At room temperature, 91 mg (0.9 mmol) of triethylamine are dissolved in 1.5 ml of dimethylformamide and stirred for 5 min. In this solution, are successively added 190 mg (0.9 mmol) of 2-(2-methylphenyl)-piperidine hydrochloride, 142 mg (0.9 mmol) of 5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxylic acid and 122 mg (0.9 mmol) of 1-hydroxybenzotriazole. The solution is poured over a 12 ml cartridge containing 2 g of Si-DCC (loading of 0.98 mmol of DCC per gram of resin) and left overnight. The cartridge is then eluted by 10 ml of dichloromethane and the organic phase is filtered over a basic alumina cartridge (2 g). The solvents are removed and the crude amide is purified by column chromatography on silica gel (gradient heptane/ethyl acetate) to yield 136 mg (45% yield) of pure (5-fluoro-1,3-dimethyl-1H-pyrazol-4-yl)[2-(2-methylphenyl)piperidin-1-yl]methanone as an oil (M+H=316).

GENERAL PREPARATION EXAMPLE 2 Thionation of Amide of Formula (I) on Chemspeed™ Apparatus

In a 13 ml Chemspeed™ vial is weighted 0.27 mmole of phosphorous pentasulfide (P₂S₅). 3 ml of a 0.18 molar solution of the amide (I) (0.54 mmol) in dioxane is added and the mixture is heated at reflux for two hours. The temperature is then cooled to 80° C. and 2.5 ml of water are added. The mixture is heated at 80° C. for one more hour. 2 ml of water are then added and the reaction mixture is extracted twice by 4 ml of dichloromethane. The organic phase is deposited on a basic alumina cartridge (2 g) and eluted twice by 8 ml of dichloromethane. The solvents are removed and the crude thioamide derivative is analyzed by LCMS and NMR. Insufficiently pure compounds are further purified by preparative LCMS.

EXAMPLE A In Vivo Preventive Test on Sphaerotheca fuliginea (Cucumber)

Solvent: 49 parts by weight of N,N-dimethylformamide

Emulsifier: 1 part by weight of Alkylarylpolyglycolether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

To test for preventive activity, young plants are sprayed with the preparation of active compound at the stated rate of application. One day after this treatment, the plants are inoculated with an aqueous spore suspension of Sphaerotheca fuliginea. Then the plants are placed in a greenhouse at approximately 23° C. and a relative atmospheric humidity of approximately 70%.

The test is evaluated 7 days after the inoculation. 0% means an efficacy which corresponds to that of the untreated control, while an efficacy of 100% means that no disease is observed.

Under these conditions, good (at least 70%) to total protection is observed at a dose of 500 ppm of active ingredient with the following compounds from table A:

TABLE A Example Efficacy 1 95 4 95 6 95 7 100 9 93 10 95 11 95 30 100 36 89 37 70 41 100 42 100 44 89 48 100 49 98 56 79 57 70 68 83 73 85 81 94 82 79 83 94 88 94 91 95 92 100 95 91 97 96 98 100 115 95 122 94 123 88 126 95 136 98 138 98 139 95 140 100 156 75 162 100 163 98 165 100 166 100 196 70

EXAMPLE B In Vivo Preventive Test on Alternaria solani (Tomato)

Solvent: 49 parts by weight of N,N-dimethylformamide

Emulsifier: 1 part by weight of Alkylarylpolyglycolether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

To test for preventive activity, young plants are sprayed with the preparation of active compound at the stated rate of application. One day after this treatment, the plants are inoculated with an aqueous spore suspension of Alternaria solani. The plants remain for one day in an incubation cabinet at approximately 22° C. and a relative atmospheric humidity of 100%. Then the plants are placed in an incubation cabinet at approximately 20° C. and a relative atmospheric humidity of 96%.

The test is evaluated 7 days after the inoculation. 0% means an efficacy which corresponds to that of the untreated control while an efficacy of 100% means that no disease is observed.

Under these conditions, good (at least 70%) to total protection is observed at a dose of 500 ppm of active ingredient with the following compounds from table B:

TABLE B Example Efficacy 1 95 4 95 5 90 6 100 7 95 8 94 9 95 10 90 11 100 34 90 36 95 37 95 40 95 41 100 42 100 43 95 44 95 47 100 48 100 49 100 51 95 53 90 54 95 55 95 56 100 57 100 58 78 59 78 60 94 65 90 67 95 68 80 71 80 72 95 73 95 76 90 80 100 81 100 82 95 83 95 86 90 87 95 88 95 90 90 91 100 92 95 92 100 93 90 94 100 95 100 96 100 97 100 98 100 99 90 103 80 104 100 105 100 110 78 112 94 113 94 114 90 115 100 116 78 117 95 118 95 120 80 121 80 122 100 123 90 124 95 125 90 129 95 132 90 134 100 135 95 136 100 137 100 138 100 139 95 140 100 141 90 142 94 143 80 144 100 145 75 146 95 147 100 148 94 149 95 150 100 151 95 153 100 154 89 155 78 156 100 157 100 160 90 162 100 163 100 164 89 165 90 166 100 169 100 172 80 173 100 176 90 177 100 179 95 180 80 181 100 182 100 183 95 184 95 185 100 186 80 187 95 188 70 189 100 190 90 191 100 194 100 195 100 196 100

EXAMPLE C In Vivo Preventive Test on Pyrenophora teres (Barley)

Solvent: 49 parts by weight of N,N-dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

To test for preventive activity, young plants are sprayed with the preparation of active compound at the stated rate of application. One day after this treatment, the plants are inoculated with an aqueous spore suspension of Pyrenophora teres.

The plants remain for 48 hours in an incubation cabinet at 22° C. and a relative atmospheric humidity of 100%. Then the plants are placed in a greenhouse at a temperature of approximately 20° C. and a relative atmospheric humidity of approximately 80%.

The test is evaluated 7-9 days after the inoculation. 0% means an efficacy which corresponds to that of the untreated control while an efficacy of 100% means that no disease is observed.

Under these conditions, good (at least 70%) to total protection is observed at a dose of 500 ppm of active ingredient with the following compounds from table C:

TABLE C Example Efficacy 1 100 3 80 4 100 5 95 6 100 7 100 8 90 9 100 10 100 11 100 12 90 30 100 34 100 36 100 37 95 40 95 41 100 42 100 43 100 44 100 46 90 47 100 48 100 49 100 49 100 50 100 51 100 53 95 54 100 55 80 56 100 57 100 59 70 60 80 64 95 65 100 67 90 68 95 70 80 71 80 72 95 73 100 76 100 78 100 79 80 80 95 81 100 82 90 83 100 84 90 86 90 87 100 88 95 90 95 91 100 92 100 93 95 94 70 95 95 96 100 97 100 98 100 99 100 100 70 102 100 103 95 104 95 105 100 113 90 114 80 115 100 117 95 118 100 120 70 121 90 122 100 123 100 124 100 125 80 129 100 131 100 132 90 134 100 135 94 136 100 137 100 138 100 139 100 140 100 142 95 144 100 145 80 147 100 148 95 149 95 150 100 153 100 154 100 156 100 157 100 159 90 160 100 161 94 162 100 163 100 164 100 165 100 166 100 169 100 172 90 173 95 176 95 177 95 179 100 180 80 181 100 182 100 183 100 184 100 185 95 186 95 187 95 188 95 189 95 190 95 191 100 194 100 195 95 196 100

EXAMPLE D In Vivo Preventive Test on Venturia inaequalis (Apple Scab)

Solvent: 24.5 parts by weight of acetone

-   -   24.5 parts by weight of N,N-dimethylacetamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

To test for preventive activity, young plants are sprayed with the preparation of active compound at the stated rate of application. After the spray coating has dried on, the plants are inoculated with an aqueous conidia suspension of the causal agent of apple scab (Venturia inaequalis) and then remain for 1 day in an incubation cabinet at approximately 20° C. and a relative atmospheric humidity of 100%.

The plants are then placed in a greenhouse at approximately 21° C. and a relative atmospheric humidity of approximately 90%.

The test is evaluated 10 days after the inoculation. 0% means an efficacy which corresponds to that of the untreated control, while an efficacy of 100% means that no disease is observed.

Under these conditions, excellent (at least 98%) to total protection is observed at a dose of 100 ppm of active ingredient with the following compounds from table D:

TABLE D Example Efficacy 1 99 10 100 11 100 30 100 54 98 67 100 136 100 140 100 165 99

EXAMPLE E In Vivo Preventive Test on Uromyces appendiculatus (Bean Rust)

Solvent: 24.5 parts by weight of acetone

-   -   24.5 parts by weight of N,N-dimethylacetamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

To test for preventive activity, young plants are sprayed with the preparation of active compound at the stated rate of application. After the spray coating has dried on, the plants are inoculated with an aqueous spore suspension of the causal agent of bean rust (Uromyces appendiculatus) and then remain for 1 day in an incubation cabinet at approximately 20° C. and a relative atmospheric humidity of 100%.

The plants are then placed in a greenhouse at approximately 21° C. and a relative atmospheric humidity of approximately 90%.

The test is evaluated 10 days after the inoculation. 0% means an efficacy which corresponds to that of the untreated control, while an efficacy of 100% means that no disease is observed.

Under these conditions, good (at least 70%) to total protection is observed at a dose of 100 ppm of active ingredient with the following compounds from table E:

TABLE E Example Efficacy 1 100 10 100 11 98 54 96 67 95 136 78 140 94 165 73

EXAMPLE F In Vivo Preventive Test on Septoria tritici (Wheat)

Solvent: 49 parts by weight of N,N-dimethylacetamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound or active compound combination is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

To test for preventive activity, young plants are sprayed with the preparation of active compound or active compound combination at the stated rate of application.

After the spray coating has been dried, the plants are sprayed with a spore suspension of Septoria tritici. The plants remain for 48 hours in an incubation cabinet at approximately 20° C. and a relative atmospheric humidity of approximately 100% and afterwards for 60 hours at approximately 15° C. in a translucent incubation cabinet at a relative atmospheric humidity of approximately 100%.

The plants are placed in the greenhouse at a temperature of approximately 15° C. and a relative atmospheric humidity of approximately 80%.

The test is evaluated 21 days after the inoculation. 0% means an efficacy which corresponds to that of the untreated control, while an efficacy of 100% means that no disease is observed.

Under these conditions, good (at least 70%) to total protection is observed at a dose of 500 ppm of active ingredient with the following compounds from table F:

TABLE F Example Efficacy 1 100 4 100 10 70 11 100 30 100 36 80 37 80 43 80 44 90 51 100 53 90 54 100 73 80 76 100 78 89 83 80 86 78 87 89 88 89 95 100 117 90 118 100 136 100 140 100 162 100 176 70

EXAMPLE G In Vivo Preventive Test on Blumeria graminis (Barley)

Solvent: 49 parts by weight of N,N-dimethylacetamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound or active compound combination is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

To test for preventive activity, young plants are sprayed with the preparation of active compound or active compound combination at the stated rate of application.

After the spray coating has been dried, the plants are dusted with spores of Blumeria graminis f. sp. hordei.

The plants are placed in the greenhouse at a temperature of approximately 18° C. and a relative atmospheric humidity of approximately 80% to promote the development of mildew pustules.

The test is evaluated 7 days after the inoculation. 0% means an efficacy which corresponds to that of the untreated control, while an efficacy of 100% means that no disease is observed.

Under these conditions, good (at least 70%) to total protection is observed at a dose of 500 ppm of active ingredient with the following compounds from table G:

TABLE G Example Efficacy 1 89 4 78 10 88 11 80 30 100 53 70 54 70 95 100 136 100 140 100 162 94

EXAMPLE H In Vivo Preventive Test on Leptosphaeria nodorum (Wheat)

Solvent: 49 parts by weight of N,N-dimethylacetamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound or active compound combination is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

To test for preventive activity, young plants are sprayed with the preparation of active compound or active compound combination at the stated rate of application. After the spray coating has been dried, the plants are sprayed with a spore suspension of Leptosphaeria nodorum.

The plants remain for 48 hours in an incubation cabinet at approximately 20° C. and a relative atmospheric humidity of approximately 100%.

The plants are placed in the greenhouse at a temperature of approximately 22° C. and a relative atmospheric humidity of approximately 80%.

The test is evaluated 8 days after the inoculation. 0% means an efficacy which corresponds to that of the untreated control, while an efficacy of 100% means that no disease is observed.

Under these conditions, good (at least 70%) to total protection is observed at a dose of 500 ppm of active ingredient with the following compounds from table H:

TABLE H Example Efficacy 10 71 30 90 53 78 54 100 78 78 95 89 136 100 140 93 162 90

EXAMPLE I In Vivo Preventive Test on Puccinia triticina (Wheat)

Solvent: 49 parts by weight of N,N-dimethylacetamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound or active compound combination is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

To test for preventive activity, young plants are sprayed with the preparation of active compound or active compound combination at the stated rate of application. After the spray coating has been dried, the plants are sprayed with a spore suspension of Puccinia triticina.

The plants remain for 48 hours in an incubation cabinet at approximately 20° C. and a relative atmospheric humidity of approximately 100%.

The plants are placed in the greenhouse at a temperature of approximately 20° C. and a relative atmospheric humidity of approximately 80%.

The test is evaluated 8 days after the inoculation. 0% means an efficacy which corresponds to that of the untreated control, while an efficacy of 100% means that no disease is observed.

Under these conditions, good (at least 70%) to total protection is observed at a dose of 500 ppm of active ingredient with the following compounds from table I:

TABLE I Example Efficacy 10 88 11 100 30 100 53 71 54 100 95 71 162 100

EXAMPLE J In Vivo Preventive Test on Fusarium nivale (Wheat)

Solvent: 49 parts by weight of N,N-dimethylacetamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound or active compound combination is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

To test for preventive activity, young plants are sprayed with the preparation of active compound or active compound combination at the stated rate of application.

After the spray coating has been dried, the plants are slightly injured by using a sandblast and afterwards they are sprayed with a conidia suspension of Fusarium nivale (var. majus).

The plants are placed in the greenhouse under a translucent incubation cabinet at a temperature of approximately 10° C. and a relative atmospheric humidity of approximately 100%.

The test is evaluated 5 days after the inoculation. 0% means an efficacy which corresponds to that of the untreated control, while an efficacy of 100% means that no disease is observed.

Under these conditions, good (at least 70%) to total protection is observed at a dose of 500 ppm of active ingredient with the following compounds from table J:

TABLE J Example Efficacy 10 88 11 83 30 100 53 100 54 71 95 100 136 86 140 71

EXAMPLE K In Vivo Protective Test on Phakopsora pachyrhizi (Soybeans)

Solvent: 28.5 parts by weight of acetone

Emulsifier: 1.5 part by weight of polyoxyethylene alkyl phenyl ether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

To test for protective activity, young plants are sprayed with the preparation of active compound at the stated rate of application. One day after spraying, the plants are inoculated with an aqueous spore suspension of the causal agent of soybean rust (Phakopsora pachyrhizi). The plants are then placed in a greenhouse at approximately 20° C. and a relative atmospheric humidity of approximately 80%.

The test is evaluated 11 days after the inoculation. 0% means an efficacy which corresponds to that of the control, while an efficacy of 100% means that no disease is observed.

Under these conditions, high (at least 90%) is observed at a dose of 250 ppm of active ingredient with the following compounds from table K:

TABLE K Example Efficacy 10 98 11 96 67 90 

The invention claimed is:
 1. A compound of formula (I):

wherein A is selected from the group consisting of: a heterocycle of formula (A¹²)

wherein: R³¹ represents a hydrogen atom or non-substituted C₁-C₅-alkyl; R³² and R³³ can be the same or different and represent a hydrogen atom; a halogen atom; non-substituted C₁-C₅-alkyl; or C₁-C₅-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different; a heterocycle of formula (A¹³)

wherein: R³⁴ and R³⁵ can be the same or different and represent a hydrogen atom; a halogen atom; non-substituted C₁-C₅-alkyl; or C₁-C₅-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different; R³⁶ represents a hydrogen atom or non-substituted C₁-C₅-alkyl; a heterocycle of formula (A¹⁴)

wherein: R³⁷ and R³⁸ can be the same or different and represent a hydrogen atom; a halogen atom; non-substituted C₁-C₅-alkyl; or C₁-C₅-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different; R³⁹ represents a hydrogen atom or non-substituted C₁-C₅-alkyl; T represents O or S; n represents 0, 1 or 2; Q¹ represents a bond; or O; B represents a phenyl ring that can be substituted by up to 5 groups X which can be the same or different; a naphthyl ring that can be substituted by up to 7 groups X which can be the same or different; or a saturated, partially saturated or unsaturated, monocyclic or fused bicyclic, 5-, 6-, 9-, 10-membered ring comprising from 1 up to 2 heteroatoms selected in the list consisting of N, O, S, that can be substituted by up to 6 groups X which can be the same or different; X represents a halogen atom; non-substituted C₁-C₅-alkyl; C₁-C₈-halogenoalkyl having 1 to 5 halogen atoms; non-substituted C₁-C₈-alkoxy; C₁-C₈-halogenoalkoxy having 1 to 5 halogen atoms; phenyl that can be substituted by up to 6 groups Q which can be the same or different; phenoxy that can be substituted by up to 6 groups Q which can be the same or different; or two substituent X together with the consecutive carbon atoms to which they are linked can form a 5- or 6-membered, saturated carbocycle or saturated heterocycle, which can be substituted by up to four groups Q which can be the same or different; Z¹ and Z² independently represent a hydrogen atom; non-substituted C₁-C₅-alkyl; C₁-C₈-halogenoalkyl having 1 to 5 halogen atoms; Z³ represents a hydrogen atom; or non-substituted C₁-C₈-alkyl; Q independently represents a halogen atom; non-substituted C₁-C₈-alkyl; C₁-C₈-halogenoalkyl having 1 to 9 halogen atoms that can be the same or different; as well as its salts, N-oxides, metal complexes, metalloid complexes and optically active isomers.
 2. A compound according to claim 1 wherein A is A¹³.
 3. A compound according to claim 1 wherein A represents A¹³ wherein R³⁴ represents a non-substituted C₁-C₅-alkyl, C₁-C₅-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different; R³⁵ represents a hydrogen atom or a halogen atom and R³⁶ represents a non-substituted C₁-C₅-alkyl.
 4. A compound according to claim 1 wherein A represents A¹³ wherein R³⁴ represents C₁-C₅-alkyl, C₁-C₅-halogenoalkyl comprising up to 3 halogen atoms that can be the same or different; R³⁵ represents a hydrogen atom; a chlorine atom; or a fluorine atom; and R³⁶ represents a methyl.
 5. A compound according to claim 1 wherein T represents O.
 6. A compound according to claim 1 wherein n represents 0 or
 1. 7. A compound according to claim 1 wherein Q¹ represents a bond.
 8. A compound according to claim 1 wherein B represents a substituted or non-substituted phenyl ring; a substituted or non-substituted naphthyl ring; a substituted or non-substituted pyridyl ring; a substituted or non-substituted thienyl ring; or a substituted or non-substituted benzothienyl ring.
 9. A compound according to claim 8 wherein B represents a substituted or non-substituted phenyl ring.
 10. A compound according to claim 8 wherein B represents a substituted or non-substituted naphthyl ring.
 11. A compound according to claim 1 wherein X independently represents a halogen atom; non-substituted C₁-C₈-alkyl; C₁-C₈-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different; non-substituted C₁-C₈-alkoxy or C₁-C₈-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different; or wherein two consecutive substituents X together with the phenyl ring form a substituted or non substituted 1,3-benzodioxolyl or 1,4-benzodioxanyl ring.
 12. A compound according to claim 1 wherein Z³ represents a hydrogen atom.
 13. A fungicide composition comprising, as an active ingredient, an effective amount of a compound of formula (I) according to claim 1 and an agriculturally acceptable support, carrier or filler.
 14. A method for controlling phytopathogenic fungi of crops, characterized in that an agronomically effective and substantially non-phytotoxic quantity of a compound according to claim 1, is applied to the soil where plants grow or are capable of growing, to the leaves and/or the fruit of plants or to the seeds of plants.
 15. A method for controlling phytopathogenic fungi of crops, characterized in that an agronomically effective and substantially non-phytotoxic quantity of a fungicide composition according to claim 13, is applied to the soil where plants grow or are capable of growing, to the leaves and/or the fruit of plants or to the seeds of plants. 